JP7225804B2 - Composition - Google Patents

Description

The present invention relates to compositions.

For example, in the field of organic thin-film transistors, compositions that cure at low temperatures are desired as compositions for insulating layers.
The low-temperature curing composition includes a reaction product of 2-isocyanatoethyl methacrylate and diethyl malonate, styrene, methyl methacrylate, 2-butyl acrylate, and 2-hydroxyethyl methacrylate. and a composition obtained by copolymerization in the presence of cyclohexanone has been reported (Patent Document 1).

JP-A-10-316643

However, the composition described in Patent Document 1 above does not necessarily have sufficient storage stability under room temperature conditions.

An object of the present invention is to provide a composition with good storage stability under room temperature conditions.

That is, embodiments of the present invention provide the inventions described in [1] to [6] below.
[1] a polymer compound (A) having a repeating unit represented by the following formula (1);
a polymer compound (B) having a repeating unit represented by the following formula (2);
A composition containing a compound represented by the following formula (3).

（１）
（式（１）中、
Ｒ^１、Ｒ^２及び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及びＲ^５は、互いに異なっていてもよく、炭素原子数１～２０のアルキル基、又は炭素原子数３～２０のシクロアルキル基を表す。該アルキル基、又はシクロアルキル基中の水素原子は、炭素原子数３～２０のシクロアルキル基、炭素原子数１～２０のアルコキシ基、炭素原子数３～２０のシクロアルコキシ基、炭素原子数６～２０の１価の芳香族炭化水素基、又はフッ素原子で置換されていてもよい。
Ｒ^ａは、炭素原子数１～２０の２価の有機基を表す。
Ｘは、酸素原子、又は－ＮＲ^ｎ－で表される基を表す。Ｒ^ｎは、水素原子又は炭素原子数１～２０の１価の有機基を表す。
ｌは、１～６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。
＊は、結合位置を表す。）

(1)
(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 and R ⁵ may be different from each other and represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. The hydrogen atom in the alkyl group or cycloalkyl group is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or 6 carbon atoms. It may be substituted with ∼20 monovalent aromatic hydrocarbon groups or fluorine atoms.
R ^a represents a divalent organic group having 1 to 20 carbon atoms.
X represents an oxygen atom or a group represented by -NR ⁿ -. R ⁿ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
l represents an integer of 1 to 6;
When there are multiple ^Ras , they may be different from each other.
* represents a binding position. )

（２）
（式（２）中、
Ｒ^６、Ｒ^７及びＲ^８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－で表される基を表す。－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、及び－ＮＨＣＯＯ－で表される基の２つの結合手は、どちらが、Ｒ^６が結合する炭素原子側に位置していてもよい。
Ｒ^ｃは、単結合、又は炭素原子数１～２０の２価の有機基を表す。
ｍは、０～６の整数を表す。
Ｒ^ｂが複数個ある場合、それらは互いに異なっていてもよい。
＊は、結合位置を表す。）

(2)
(In formula (2),
R ⁶ , R ⁷ and R ⁸ 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-, represented by -NHCO- or a group represented by -NHCOO-. Two bonds of a group represented by -O-, a group represented by -CO-, a group represented by -COO-, a group represented by -NHCO-, and a group represented by -NHCOO- may be located on the carbon atom side to which R ⁶ is bonded.
R ^c represents a single bond or a divalent organic group having 1 to 20 carbon atoms.
m represents an integer from 0 to 6;
When there are multiple Rb ^'s , they may be different from each other.
* represents a binding position. )

（３）
（式（３）中、
Ｒ^９は、炭素原子数１～２０のアルキル基、炭素原子数３～２０のシクロアルキル基、又は炭素原子数２～２０の下記式（６）で表される基を表す。該アルキル基、シクロアルキル基、又は下記式（６）で表される基中の水素原子は、炭素原子数３～２０のシクロアルキル基、炭素原子数１～２０のアルコキシ基、炭素原子数３～２０のシクロアルコキシ基、炭素原子数６～２０の１価の芳香族炭化水素基、又はフッ素原子で置換されていてもよい。）

(3)
(In formula (3),
R ⁹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a group represented by the following formula (6) having 2 to 20 carbon atoms. The hydrogen atom in the alkyl group, cycloalkyl group, or group represented by the following formula (6) is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms. It may be substituted with a cycloalkoxy group having up to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a fluorine atom. )

（６）
（式（６）中、
Ｒ^１５は、炭素原子数１～６の２価の直鎖状脂肪族炭化水素基を表し、
Ｒ^１６は、炭素原子数１～１９の１価の直鎖状脂肪族炭化水素基を表し、
ｑは、１～１９の整数を表す。
ただし、Ｒ^１５、Ｒ^１６、及びｑは、全体の炭素原子数が２～２０になるように調整される。）
［２］ 前記高分子化合物（Ａ）、及び前記高分子化合物（Ｂ）からなる群より選ばれる少なくとも一種の高分子化合物が、下記式（４）で表される繰り返し単位をさらに含む高分子化合物である、［１］に記載の組成物。

(6)
(In formula (6),
R ¹⁵ represents a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms,
R ¹⁶ represents a monovalent linear aliphatic hydrocarbon group having 1 to 19 carbon atoms,
q represents an integer from 1 to 19;
However, R ¹⁵ , R ¹⁶ and q are adjusted so that the total number of carbon atoms is 2-20. )
[2] A polymer compound in which at least one polymer compound selected from the group consisting of the polymer compound (A) and the polymer compound (B) further comprises a repeating unit represented by the following formula (4): The composition according to [1].

（４）
（式（４）中、
Ｒ^１０、Ｒ^１１、及びＲ^１２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^１３は、塩素原子、フッ素原子、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。
Ｒ^ｄ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－で表される基を表す。これらの－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、及び－ＮＨＣＯＯ－で表される基の２つの結合手は、どちらが、Ｒ^１０が結合する炭素原子側に位置していてもよい。Ｒ^ｄで表される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。
ｎ１は、０～５の整数を表す。
ｎ２は、０～６の整数を表す。
Ｒ^ｄ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^１３が複数個ある場合、それらは互いに異なっていてもよい。
＊は、結合位置を表す。）
［３］ 前記式（３）中、Ｒ^９が、炭素原子数１～２０のアルキル基、又は炭素原子数３～２０のシクロアルキル基である（該アルキル基、又はシクロアルキル基中の水素原子は、炭素原子数３～２０のシクロアルキル基、炭素原子数１～２０のアルコキシ基、炭素原子数３～２０のシクロアルコキシ基、又は、炭素原子数６～２０の１価の芳香族炭化水素基で置換されていてもよい。）、［１］又は［２］に記載の組成物。
［４］ 組成物に含まれる前記式（３）で表される化合物が、１質量％以上９０質量％以下である、［１］～［３］のいずれか１つに記載の組成物。
［５］ 電子デバイスに用いられる、［１］～［４］のいずれか１つに記載の組成物を含む、絶縁層用組成物。
［６］ 前記電子デバイスが有機薄膜トランジスタである、［５］に記載の絶縁層用組成物。
［７］ ［１］～［４］のいずれか１つに記載の組成物が硬化した膜をゲート絶縁層として含む、有機薄膜トランジスタ。

(4)
(In formula (4),
R ¹⁰ , R ¹¹ and R ¹² 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 ¹³ represents a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, or a monovalent organic group having 1 to 20 carbon atoms.
R ^d 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-, represented by -NHCO- or a group represented by -NHCOO-. These groups represented by -O-, groups represented by -CO-, groups represented by -COO-, groups represented by -NHCO-, and groups represented by -NHCOO- Either bond may be located on the carbon atom side to which R ¹⁰ is bonded. A hydrogen atom in the divalent organic group represented by ^Rd may be substituted with a fluorine atom.
n1 represents an integer of 0 to 5;
n2 represents an integer of 0-6.
When there are multiple Rd ^'s , they may be different from each other.
When there are multiple R ¹³ , they may be different from each other.
* represents a binding position. )
[3] In the above formula (3), R ⁹ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms (the hydrogen atom in the alkyl group or cycloalkyl group is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. may be substituted with a group.), the composition according to [1] or [2].
[4] The composition according to any one of [1] to [3], wherein the compound represented by the formula (3) contained in the composition is 1% by mass or more and 90% by mass or less.
[5] A composition for an insulating layer, comprising the composition according to any one of [1] to [4], for use in electronic devices.
[6] The composition for insulating layer according to [5], wherein the electronic device is an organic thin film transistor.
[7] An organic thin film transistor comprising a film obtained by curing the composition according to any one of [1] to [4] as a gate insulating layer.

According to the present invention, it is possible to provide a composition having high storage stability even under room temperature conditions.

1 is a schematic diagram schematically showing the structure of a bottom-gate top-contact type organic thin film transistor; FIG. 1 is a schematic diagram schematically showing the structure of a bottom-gate bottom-contact type organic thin film transistor; FIG. 1 is a schematic diagram schematically showing the structure of a top-gate bottom-contact type organic thin film transistor; FIG.

Next, embodiments of the present invention will be described in further detail. It should be noted that each of the referenced drawings only schematically shows the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited by the following description, and each component can be changed as appropriate without departing from the gist of the present invention. In the drawings used for explanation, the same components are denoted by the same reference numerals, and duplicate explanations may be omitted. Also, configurations according to embodiments of the present invention are not necessarily manufactured or used in the arrangement shown in the drawings.

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

A "polymer compound" means a compound containing a plurality of structural units (repeating units) that may be different from each other in the molecule, and so-called dimers are also included in the "polymer compound". Also, as used herein, the term "low-molecular-weight compound" means a compound that does not contain a plurality of structural units in its molecule.

The monovalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. good.

Examples of monovalent organic groups having 1 to 20 carbon atoms include:
Monovalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, monovalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, monovalent alicyclic group having 3 to 20 carbon atoms Hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms , an alkoxycarbonyl group having 2 to 20 carbon atoms, and an aryloxycarbonyl group having 7 to 20 carbon atoms.
These groups are those in which the hydrogen atoms in the group are alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and It may be substituted with a cycloalkoxy group, a monovalent hydrocarbon group having 6 to 20 carbon atoms, or a halogen atom.

The monovalent organic group is preferably
Monovalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, monovalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, monovalent alicyclic group having 3 to 6 carbon atoms Hydrocarbon group, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, alkoxy group having 1 to 6 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acyl group having 2 to 7 carbon atoms , an alkoxycarbonyl group having 2 to 7 carbon atoms, and an aryloxycarbonyl group having 7 to 20 carbon atoms.
These groups are those in which the hydrogen atoms in the group are alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and It may be substituted with a cycloalkoxy group, a monovalent hydrocarbon group having 6 to 20 carbon atoms, or a halogen atom.

Specific examples of monovalent organic groups 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, 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, pentafluorophenyl group, trifluoromethylphenyl group, chlorophenyl group, bromophenyl group , methoxy group, ethoxy group, phenoxy group, acetyl group, benzoyl group, methoxycarbonyl group, phenoxycarbonyl group, benzyl group and the like.

The monovalent organic group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be linear or branched.
Examples of alkyl groups having 1 to 20 carbon atoms include
methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3 , 7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyldecyl group and dodecyl group.

The alkyl group having 1 to 20 carbon atoms, as a substituent, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, and a cycloalkoxy group having 3 to 20 carbon atoms. It may have 6 to 20 monovalent aromatic hydrocarbon groups or fluorine atoms.
Examples of substituted alkyl groups having 1 to 20 carbon atoms include:
trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, benzyl group, 2-phenylethyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group , 3-(3,5-di-hexylphenyl)propyl group, 6-ethyloxyhexyl group, methoxymethyl group and ethoxyethyl group.

Examples of cycloalkyl groups having 3 to 20 carbon atoms include
A cyclopentyl group and a cyclohexyl group are mentioned.
A cycloalkyl group having 3 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, and a cycloalkoxy group having 3 to 20 carbon atoms as a substituent. It may have 6 to 20 monovalent aromatic hydrocarbon groups or fluorine atoms.

The divalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. good.

Examples of divalent organic groups having 1 to 20 carbon atoms include:
Divalent straight-chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, branched divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, divalent alicyclic group having 3 to 20 carbon atoms Examples include hydrocarbon groups and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.
These groups are alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and cyclo It may be substituted with an alkoxy group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogen atom.

Among them, as a divalent organic group having 1 to 20 carbon atoms,
divalent straight-chain aliphatic hydrocarbon group having 1 to 6 carbon atoms, branched divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms, divalent alicyclic group having 3 to 6 carbon atoms A hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms are preferred.
These groups are alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and cyclo It may be substituted with an alkoxy group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a halogen atom.

Specific examples of divalent aliphatic hydrocarbon groups and divalent alicyclic hydrocarbon groups include:
methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2 -methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, cyclopentylene group, n-hexylene group, 1-methyl-n-pentylene group, Cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group and the like.

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

A halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the formula, * indicates the bonding position of the repeating unit.

<Composition>
The composition of the present invention comprises a polymer compound (A) having a repeating unit represented by formula (1), a polymer compound (B) having a repeating unit represented by formula (2), and ) and the compound represented by.
Each of the polymer compound (A) and the polymer compound (B) contained in the composition may be one type or two or more types.
In the composition, the compound represented by the formula (3) is a solvent, and the polymer compound (A) and the polymer compound (B) are dissolved in the compound represented by the formula (3). is preferred.

(Polymer compound (A))
Here, the polymer compound (A) will be described.

The polymer compound (A) preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 500,000.

The polymer compound (A) may be linear, branched, or cyclic.

Polymer compound (A) has a repeating unit represented by formula (1).

(Repeating unit represented by formula (1))

（１）
（式（１）中、
Ｒ^１、Ｒ^２及び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及びＲ^５は、互いに異なっていてもよく、炭素原子数１～２０のアルキル基、又は炭素原子数３～２０のシクロアルキル基を表す。該アルキル基、又はシクロアルキル基中の水素原子は、炭素原子数３～２０のシクロアルキル基、炭素原子数１～２０のアルコキシ基、炭素原子数３～２０のシクロアルコキシ基、炭素原子数６～２０の１価の芳香族炭化水素基、又はフッ素原子で置換されていてもよい。
Ｒ^ａは、炭素原子数１～２０の２価の有機基を表す。
Ｘは、酸素原子、又は－ＮＲ^ｎ－で表される基を表す。Ｒ^ｎは、水素原子又は炭素原子数１～２０の１価の有機基を表す。
ｌは、１～６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。
＊は、結合位置を表す。）

(1)
(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 and R ⁵ may be different from each other and represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. The hydrogen atom in the alkyl group or cycloalkyl group is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or 6 carbon atoms. It may be substituted with ∼20 monovalent aromatic hydrocarbon groups or fluorine atoms.
R ^a represents a divalent organic group having 1 to 20 carbon atoms.
X represents an oxygen atom or a group represented by -NR ⁿ -. R ⁿ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
l represents an integer of 1 to 6;
When there are multiple ^Ras , they may be different from each other.
* represents a binding position. )

In formula (1), R ¹ , R ² and R ³ are each independently preferably a hydrogen atom or a methyl group.

In the above formula (1), X is preferably an oxygen atom or a group represented by -NH-.

In formula (1) above, R ^a is preferably a methylene group, an ethylene group, an n-propylene group, or an n-butylene group.

In formula (1), R ⁴ and R ⁵ are each independently preferably a methyl group or an ethyl group.

Examples of monomers that are raw materials for the repeating unit represented by formula (1) include 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate.
A monomer that is a starting material for the repeating unit represented by formula (1) can be produced by a known method. For example, it can be produced by reacting a compound represented by the following formula (5) with a malonic acid ester. can be done.

（式（５）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^ａ、Ｘ、及びｌは、上記と同じ意味を表す。）

(In formula (5), R ¹ , R ² , R ³ , R ^a , X, and l have the same meanings as above.)

Compounds of formula (5) include 2-methacryloyloxyethyl isocyanate and a 1:1 reaction product of 2-hydroxyethyl (meth)acrylate and a diisocyanato compound.
Diisocyanato compounds to be reacted with 2-hydroxyethyl (meth)acrylate include, for example, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, 3, 5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (I PDI), m- or p-xylylene diisocyanate (m- or p-X D I ), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1 ,3- or 1,4-bis(isocyanatomethyl)cyclohexane, lysine diisocyanate and the like can be used.
As the compound represented by formula (5), 2-methacryloyloxyethyl isocyanate is preferable from the standpoint of availability and handling of high-purity products, and 2-methacryloyloxyethyl isocyanate is more preferable from the standpoint of reactivity.

Malonic acid esters to be reacted with the compound of formula (5) are preferably malonic acid dimethyl ester and malonic acid diethyl ester, for example.
Malonic esters include aliphatic alcohols (e.g., methanol, ethanol, iso- and n-propanol, various butanols, 2-ethylhexyl alcohol), alicyclic alcohols (e.g., cyclohexylmethanol), and alcohols containing aromatic rings (e.g., benzyl alcohol) and malonic acid.

Specific examples of the polymer compound (A) having a repeating unit represented by formula (1) are shown below, but the present invention is not limited thereto.

In formulas (A1) to (A26),
R ¹ , R ² and R ³ may be different from each other and represent a hydrogen atom or a methyl group.
R ⁴ and R ⁵ may be different from each other and represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and R ⁴ and R ⁵ are each independently , a methyl group, or an ethyl group.

The polymer compound (A) contained in the composition is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and 5% by mass or more and 30% by mass or less. is more preferable.

(Polymer compound (B))
Here, the polymer compound (B) will be explained.

The polymer compound (B) preferably has a weight average molecular weight of 3,000 to 1,000,000, more preferably 5,000 to 500,000.

The polymer compound (B) may be linear, branched, or cyclic.

The polymer compound (B) has a repeating unit represented by formula (2).

(Repeating unit represented by formula (2))

（２）
（式（２）中、
Ｒ^６、Ｒ^７及びＲ^８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－で表される基を表す。－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、及び－ＮＨＣＯＯ－で表される基の２つの結合手は、どちらが、Ｒ^６が結合する炭素原子側に位置していてもよい。
Ｒ^ｃは、単結合、又は炭素原子数１～２０の２価の有機基を表す。
ｍは、０～６の整数を表す。
Ｒ^ｂが複数個ある場合、それらは互いに異なっていてもよい。
＊は、結合位置を表す。）

(2)
(In formula (2),
R ⁶ , R ⁷ and R ⁸ 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-, represented by -NHCO- or a group represented by -NHCOO-. Two bonds of a group represented by -O-, a group represented by -CO-, a group represented by -COO-, a group represented by -NHCO-, and a group represented by -NHCOO- may be located on the carbon atom side to which R ⁶ is bonded.
R ^c represents a single bond or a divalent organic group having 1 to 20 carbon atoms.
m represents an integer from 0 to 6;
When there are multiple Rb ^'s , they may be different from each other.
* represents a binding position. )

In formula (2), R ⁶ , R ⁷ and R ⁸ are each independently preferably a hydrogen atom or a methyl group.
In formula (2), m is preferably an integer of 0-2.
In the above formula (2), R ^b is a group represented by -COO-, a group represented by -NHCO-, a group represented by -NHCOO-, a methylene group, an ethylene group, an n-propylene group, iso A propylene group, an n-butylene group, or a phenylene group is preferred.
In formula (2), R ^c is preferably a single bond, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, or a phenylene group.
A preferable embodiment of the formula (2) is
R ⁶ , R ⁷ and R ⁸ are a hydrogen atom or a methyl group,
m is 1;
R ^b is a group represented by -COO-,
Examples include the case where R ^c is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.

Examples of repeating units represented by formula (2) contained in the polymer compound (B) include repeating units derived from the following monomers.
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 4-hydroxymethylcyclohexyl acrylate, 2 -hydroxy-1-methylethyl acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, 2-hydroxycyclohexyl acrylate, 3-hydroxycyclohexyl acrylate, 4-hydroxycyclohexyl acrylate, 2-hydroxy-3-phenoxypropyl 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, 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, 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-hydroxy Propyl methacrylate, 2-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylates, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl methacrylate, and 2-acryloyloxyethyl-2-hydroxyethyl - (meth)acrylates with hydroxyalkyl groups such as phthalic acid,
hydroxyvinyl ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and ethylene glycol monoallyl ether;
styrene derivatives such as o-(hydroxymethyl)styrene, m-(hydroxymethyl)styrene, and p-(hydroxymethyl)styrene;
(meth)acrylamide having a hydroxyalkyl group such as N-(2-hydroxyethyl)acrylamide,
ethenyl esters such as 2-hydroxypropionic acid (1-methyl)ethenyl ester, 2-hydroxypropionic acid ethenyl ester, 3-hydroxypropionic acid ethenyl ester, and 2-hydroxyacetic acid ethenyl ester;
vinyl alcohol, as well as allyl alcohol.
As the repeating unit represented by formula (2), a repeating unit derived from (meth)acrylate having a hydroxyalkyl group is preferable.

Examples of the polymer compound (B) having a repeating unit represented by formula (2) include:
Poly(2-hydroxyethyl acrylate), poly(2-hydroxyethyl methacrylate), poly(2-hydroxybutyl methacrylate), poly(4-hydroxybutyl acrylate), poly(2-hydroxybutylacrylamide), poly(4-hydroxy butyl methacrylamide), poly(vinyl alcohol),
Poly(styrene-co-(2-hydroxyethyl acrylate)), poly(styrene-co-(2-hydroxyethyl methacrylate)), poly(styrene-co-(2-hydroxybutyl methacrylate)), poly(styrene-co -(4-hydroxybutyl acrylate)), poly(2,3,4,5,6-pentafluorostyrene-co-(2-hydroxyethyl methacrylate)), poly(2,3,4,5,6-penta Fluorostyrene-co-(4-hydroxybutyl acrylate)), Poly(benzyl methacrylate-co-(2-hydroxyethyl methacrylate)), Poly(benzyl methacrylate-co-(4-hydroxybutyl acrylate)), Poly(benzyl methacrylate) -co-(2-hydroxypropyl methacrylate)), poly(2,3,4,5,6-pentafluorobenzyl methacrylate-co-(2-hydroxybutyl methacrylate)), poly(2,3,4,5, 6-pentafluorobenzyl methacrylate-co-(2-hydroxyethyl methacrylate)), poly(2,3,4,5,6-pentafluorobenzyl methacrylate-co-(4-hydroxybutyl acrylate)), poly(methacrylic acid methyl-co-(2-hydroxyethyl methacrylate)), poly(methyl methacrylate-co-(4-hydroxybutyl acrylate)), poly(styrene-co-(2,3,4,5,6-pentafluorostyrene) )-co-[2-hydroxybutyl methacrylate]), poly(styrene-co-(2,3,4,5,6-pentafluorostyrene)-co-[2-hydroxyethyl methacrylate]), poly(styrene- co-(2,3,4,5,6-pentafluorostyrene)-co-[4-hydroxybutyl acrylate]), poly(2,2,2-trifluoroethyl methacrylate-co-(2-hydroxyethyl methacrylate) )), poly(2,2,2-trifluoroethyl methacrylate-co-(2-hydroxyethyl acrylate)), poly(2,2,2-trifluoroethyl methacrylate-co-(4-hydroxybutyl acrylate)) , poly(2,2,2-trifluoroethyl methacrylate-co-(4-hydroxybutyl methacrylate)),
Poly(styrene-co-(2,3,4,5,6-pentafluorostyrene)-co-(2-hydroxyethyl methacrylate)), poly(styrene-co-(2,3,4,5,6- pentafluorostyrene)-co-(4-hydroxybutyl acrylate)), poly(styrene-co-(2,2,2-trifluoroethyl methacrylate)-co-(2-hydroxybutyl methacrylate)), poly(styrene- co-(2,2,2-trifluoroethyl methacrylate)-co-(2-hydroxyethyl methacrylate)), poly(styrene-co-(2,2,2-trifluoroethyl methacrylate)-co-(4- hydroxybutyl methacrylate)), poly((2,3,4,5,6-pentafluorobenzyl acrylate)-co-(4-hydroxybutyl methacrylate)), poly(2,3,4,5,6-pentafluoro Styrene-co-[2-(2-hydroxyethoxy)ethyl acrylate]), poly(2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co-(3-hydroxy-1-adamantyl acrylate) ), poly (2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co-(4-hydroxycyclohexyl acrylate)), poly (2,3,4,5,6-pentafluorostyrene-co -acrylonitrile-co-allyltrimethylgermanium-co-ethylene glycol monoallyl ether), poly(styrene-co-2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co-(p-(hydroxymethyl ) styrene)), poly(styrene-co-2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co-allyltrimethylgermanium-co-(8-hydroxyoctyl methacrylate)), poly(styrene- co-2,3,4,5,6-pentafluorostyrene-co-acrylonitrile-co-allyltrimethylgermanium-co-[2-(2-hydroxyethoxy)ethyl methacrylate]), poly(methyl methacrylate-co-2 , 3,4,5,6-pentafluorostyrene-co-(3-hydroxy-1-adamantyl methacrylate)), poly(methyl methacrylate-co-2,3,4,5,6-pentafluorostyrene-(4 -hydroxymethylcyclohexyl acrylate)), poly(2,3,4,5,6-pentafluorostyrene-co-(2 ,2,2-trifluoroethyl methacrylate)-co-(4-hydroxymethylcyclohexylmethacrylate)), poly(styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-acrylonitrile-co -(2-hydroxyethyl methacrylate)), poly(styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-acrylonitrile-co-allyltrimethylgermanium-co-(2-hydroxyethyl methacrylate) ), poly(styrene-co-4-(1-ethoxyethyl)styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-(4-hydroxybutyl methacrylate)), poly(styrene- co-4-(1-ethoxyethyl)styrene-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-(4-hydroxybutyl methacrylate)), poly(styrene-co-{4-vinyl -(tetrahydro-2-pyranyl)benzoate}-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-(4-hydroxybutyl methacrylate)), poly(styrene-co-{4-vinyl- (tetrahydro-2-pyranyl)benzoate}-co-2,3,4,5,6-pentafluorobenzyl methacrylate-co-(4-hydroxybutyl methacrylate)), poly(vinyl alcohol-co-ethylene), poly( vinyl alcohol-co-vinyl acetate), poly(2-hydroxypropionic acid ethenyl ester-co-vinyl acetate), poly(styrene-co-(2-hydroxypropionic acid ethenyl ester)), and the like.

The polymer compound (B) contained in the composition is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and 5% by mass or more and 30% by mass or less. is more preferable.

(Repeating unit represented by formula (4))
Polymer compound (A) and/or (B) may contain a repeating unit represented by the following formula (4).

（４）

(4)

(In formula (4),
R ¹⁰ , R ¹¹ and R ¹² 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 ¹³ represents a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, or a monovalent organic group having 1 to 20 carbon atoms.
R ^d 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-, represented by -NHCO- or a group represented by -NHCOO-. These groups represented by -O-, groups represented by -CO-, groups represented by -COO-, groups represented by -NHCO-, and groups represented by -NHCOO- Either of the bonds may be located on the carbon atom side to which R ¹⁰ is bonded. A hydrogen atom in the divalent organic group represented by ^Rd may be substituted with a fluorine atom.
n1 represents an integer of 0 to 5;
n2 represents an integer of 0-6.
When there are multiple Rd ^'s , they may be different from each other.
When there are multiple R ¹³ , they may be different from each other.
* represents a binding position. )

In formula (4), R ¹⁰ , R ¹¹ and R ¹² are each independently preferably a hydrogen atom or a methyl group.

In the above formula (4), R ^d is preferably a divalent organic group having 1 to 20 carbon atoms or a group represented by -COO-.

In formula (4), n2 is preferably an integer of 0-2.

From the viewpoint of improving the dielectric breakdown strength of the cured film obtained by curing the composition of the present invention, the ratio of the repeating unit represented by the formula (4) contained in the polymer compound (A) and/or (B) is preferably 1 mol% or more and 90 mol% or less, and preferably 10 mol% or more and 90 mol% or less, where the total content of all repeating units contained in each polymer compound is 100 mol%. More preferably, it is 30 mol % or more and 80 mol % or less.

Examples of monomers that are raw materials for the repeating unit represented by formula (4) 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, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 4-vinyl-p-terphenyl, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α- methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, Diisopropylbenzene, 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-(methoxyethoxymethyloxycarbonyl)styrene, 3-(1- ethoxyethyloxycarbonyl)styrene, 3-(tetrahydropyranyloxycarbonyl)styrene, 4-(methoxymethoxycarbonyl)styrene, 4-(methoxyethoxymethyloxycarbonyl)styrene, 4-(1-ethoxyethyloxycarbonyl)styrene, 4-(tetrahydropyranyloxycarbonyl)styrene, benzyl acrylate, benzyl methacrylate, 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, 2,3,4,5,6-pentafluoro Styrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene Luorostyrene, 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,
phenyl acrylate, benzyl acrylate, phenyl methacrylate, benzyl methacrylate, N-phenylacrylamide, N-phenylmethacrylamide, vinyl benzoate, allyl benzoate,
2,3,4,5,6-pentafluorobenzyl acrylate, 2,3,4,5,6-pentafluorobenzyl methacrylate, 2-fluorobenzyl acrylate, 2-fluorobenzyl methacrylate, 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-(penta fluorophenyl)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)methacrylamide and the like.

(other repeating units)
The polymer compound (A) may be a polymer compound having a repeating unit represented by formula (1) and another repeating unit,
It may be a polymer compound having a repeating unit represented by formula (1), a repeating unit represented by formula (4), and other repeating units.
The polymer compound (B) may be a polymer compound having a repeating unit represented by formula (2) and another repeating unit,
It may be a polymer compound having a repeating unit represented by formula (2), a repeating unit represented by formula (4), and other repeating units.
Here, other repeating units are
It means a repeating unit other than the repeating unit represented by formula (1), the repeating unit represented by formula (2), or the repeating unit represented by formula (4).

The ratio of other repeating units contained in the polymer compound is not particularly limited, and is, for example, 0 mol% or more and 90 mol% or less, where the total content of all repeating units contained in the polymer compound is 100 mol%. , 0 mol % or more and 80 mol % or less, or 0 mol % or more and 50 mol % or less.

Examples of monomers used as raw materials for other repeating units include acrylic acid, methacrylic acid, 4-vinylbenzoic acid, acrylic acid esters and derivatives thereof, methacrylic acid esters and derivatives thereof, acrylamide and derivatives thereof, methacrylamide and derivatives thereof. , methacrylonitrile, acrylonitrile, 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, N-vinylamide derivatives of organic carboxylic acids, maleimides and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and organic germanium derivatives.

Monomers that are materials for other repeating units are appropriately selected according to the properties required for the insulating layer.
As monomers that are materials for other repeating units, it is preferable to use monomers capable of imparting flexibility, such as methacrylic acid esters and derivatives thereof, and acrylic acid esters and derivatives thereof.

Monofunctional acrylates and polyfunctional acrylates can be used as acrylic acid esters and derivatives thereof, which are monomers that serve as materials for other repeating units.
Examples of acrylic acid esters and derivatives thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and acrylic acid. Hexyl, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-cyanoethyl 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 acrylates, 1,1,1,2,2,2-hexafluoroisopropyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 2 -(perfluorodecyl) ethyl acrylate, 2-(perfluoro-3-methylbutyl) ethyl acrylate, 2-(perfluoro-5-methylhexyl) ethyl acrylate, 2-(perfluoro-7-methyloctyl) ethyl acrylate, 1H,1H,3H-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,7H-dodecafluoroheptyl acrylate, 1H,1H,9H-hexadecafluorononyl acrylate, 1H-1-( trifluoromethyl)trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate and the like.

Monofunctional methacrylates and polyfunctional methacrylates can be used as methacrylic acid esters and derivatives thereof, which are monomers used as materials for other repeating units.
Examples of methacrylic acid esters and derivatives thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and methacrylic acid. Hexyl, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 1,1 , 1,2,2,2-hexafluoroisopropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, 2-(perfluorodecyl ) ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 2-(perfluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 1H, 1H, 3H -tetrafluoropropyl methacrylate, 1H,1H,5H-octafluoropentyl methacrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate, 1H,1H,9H-hexadecafluorononyl methacrylate, 1H-1-(trifluoromethyl)tri fluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate and the like.

Examples of acrylamide and its derivatives, which are monomers used as materials for other repeating units, include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-tert-butylacrylamide, N,N-dimethylacrylamide, N,N -diethylacrylamide, N-(butoxymethyl)acrylamide, N-[3-(dimethylamino)propyl]acrylamide, N-acryloylmorpholine.

Examples of methacrylamide and its derivatives, which are monomers used as materials for other repeating units, include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-tert-butylmethacrylamide, N,N-dimethyl methacrylamide, N,N-diethylmethacrylamide, N-(butoxymethyl)methacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-acryloylmorpholine,
are mentioned.

Examples of vinyl esters of organic carboxylic acids and derivatives thereof, which are monomers for other repeating units, include vinyl acetate, vinyl propionate, vinyl butyrate, and divinyl adipate.

Examples of allyl esters of organic carboxylic acids and derivatives thereof, which are monomers used as other repeating unit materials, include allyl acetate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

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

Examples of dialkyl esters of maleic acid and derivatives thereof, which are monomers for other repeating units, include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, and maleic acid. di-n-butyl acid, di-2-ethylhexyl maleate, dibenzyl maleate and the like.

Examples of dialkyl esters of itaconic acid and derivatives thereof, which are monomers for other repeating units, include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, itaconate. di-n-butyl acid, di-2-ethylhexyl itaconate, dibenzyl itaconate and the like.

Examples of N-vinylamide derivatives of organic carboxylic acids, which are monomers used as materials for other repeating units, include N-methyl-N-vinylacetamide.

Examples of maleimide and its derivatives, which are monomers used as materials for other repeating units, include N-phenylmaleimide and N-cyclohexylmaleimide.

Examples of terminally unsaturated hydrocarbons and derivatives thereof, which are monomers used as materials for other repeating units, include 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, and the like. .

Examples of organogermanium derivatives, which are monomers that form other repeating units, include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, and triethylvinylgermanium.

Among the monomers that are used as materials for these other repeating units, acrylic acid alkyl esters, methacrylic acid alkyl esters, acrylonitrile, methacrylonitrile, or allyltrimethylgermanium are preferred.

（３）
（式（３）中、
Ｒ^９は、炭素原子数１～２０のアルキル基、炭素原子数３～２０のシクロアルキル基、又は炭素原子数２～２０の下記式（６）で表される基を表す。該アルキル基、シクロアルキル基、又は下記式（６）で表される基中の水素原子は、炭素原子数３～２０のシクロアルキル基、炭素原子数１～２０のアルコキシ基、炭素原子数３～２０のシクロアルコキシ基、炭素原子数６～２０の１価の芳香族炭化水素基、又はフッ素原子で置換されていてもよい。）(Compound represented by formula (3))

(3)
(In formula (3),
R ⁹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a group represented by the following formula (6) having 2 to 20 carbon atoms. The hydrogen atom in the alkyl group, cycloalkyl group, or group represented by the following formula (6) is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms. It may be substituted with a cycloalkoxy group having up to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a fluorine atom. )

（６）
（式（６）中、
Ｒ^１５は、炭素原子数１～６の２価の直鎖状脂肪族炭化水素基を表し、
Ｒ^１６は、炭素原子数１～１９の１価の直鎖状脂肪族炭化水素基を表し、
ｑは、１～１９の整数を表す。
ただし、Ｒ^１５、Ｒ^１６、及びｑは、全体の炭素原子数が２～２０になるように調整される。）

(6)
(In formula (6),
R ¹⁵ represents a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms,
R ¹⁶ represents a monovalent linear aliphatic hydrocarbon group having 1 to 19 carbon atoms,
q represents an integer from 1 to 19;
However, R ¹⁵ , R ¹⁶ and q are adjusted so that the total number of carbon atoms is 2-20. )

In formula (3), R ⁹ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms (the hydrogen atom in the alkyl group or cycloalkyl group has 3 carbon atoms substituted with a cycloalkyl group having up to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms; may also be used.) is preferable.

As the compound represented by formula (3),
methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol,
1-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-pentanol, 3-methyl-2-butanol, 3-pentanol, 2-methyl-2 - butanol,
1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tetradecanol, 1-octadecanol, cyclopentylmethanol, cyclohexylmethanol, benzyl alcohol, 2-phenylethanol, 3-phenylpropanol, methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol , 1-propoxy-2-propanol, 1-butoxy-2-propanol,
2,2,3,3-tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,2-trifluoroethanol, 1H,1H,3H- hexafluorobutanol, 1H,1H,5H-octafluoropentanol, 1H,1H,7H-dodecafluoroheptanol, pentafluorobenzyl alcohol and the like.

As the compound represented by formula (3), methanol, ethanol and 1-pentanol are preferable from the viewpoint of availability of high-purity products, and cyclopentanol, cyclohexanol, 2 - ethoxyethanol and benzyl alcohol are preferred.

The content of the compound represented by formula (3) in the composition is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 70% by mass or less, and 5% by mass or more. It is more preferably 60% by mass or less. It is particularly preferable to be 10% by mass or more and 50% by mass or less.

(other ingredients)
The composition of the present invention may further contain a solvent for mixing and adjusting viscosity, an additive that is usually used in combination with a cross-linking agent when cross-linking a polymer compound, and the like.

Examples of solvents that can be used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic hydrocarbon solvents such as xylene. Examples include hydrocarbon solvents, ketone solvents such as cyclopentanone, 2-heptanone and acetone, acetate solvents such as propylene glycol monomethyl ether acetate butyl acetate, halide solvents such as chloroform, and mixed solvents thereof.
As the additive, a catalyst for promoting the cross-linking reaction, a leveling agent, a viscosity modifier and the like can be used.

<Method for producing composition>
The composition of the present invention can be produced by mixing the polymer compound (A), the polymer compound (B) and the compound represented by formula (3).
The method for producing the composition includes, for example,
(M1) mixing the compound represented by formula (3) with the polymer compound (A);
It may be a production method comprising a step of mixing the resulting mixture with the polymer compound (B),
(M2) mixing the compound represented by formula (3) with the polymer compound (B);
It may be a production method comprising a step of mixing the resulting mixture with the polymer compound (A),
(M3) a step of mixing the polymer compound (A) and the polymer compound (B);
It may be a production process comprising a step of mixing the resulting mixture with the compound represented by formula (3).
From the viewpoint of the stability of the composition during the mixing step, the method for producing the composition is preferably the method for producing (M1) or (M2). A composition containing a mixture of the compound represented by formula (3) and the polymer compound (A) and the polymer compound (B) can be obtained by the production method (M1). A composition containing a mixture of the compound represented by formula (3) and the polymer compound (B) and the polymer compound (A) can be obtained by the production method of (M2).

The mixing ratio of the polymer compound (A) and the polymer compound (B) is determined by the repeating unit represented by the formula (1) of the polymer compound (A) and the formula (2) of the polymer compound (B). The molar ratio of the represented repeating unit is preferably 1/100 to 10000/100, more preferably 10/100 to 1000/100, still more preferably 50/100 to 200/100. By adjusting the charged molar ratio of the above monomers within this range, a crosslinked structure is sufficiently formed inside the cured product obtained by curing the composition of the present invention, and the solvent resistance is improved.

(Method for producing polymer compound (A))
The polymer compound (A) is prepared, for example, by a method of polymerizing a monomer (polymerizable monomer) as a raw material of the repeating unit represented by the above formula (1) using a photopolymerization initiator or a thermal polymerization initiator. can be manufactured.
When the polymer compound (A) further has at least one type selected from the group consisting of repeating units represented by formula (4) and other repeating units, raw materials for repeating units represented by formula (1) and at least one monomer selected from the group consisting of monomers that are raw materials for repeating units represented by formula (4), and monomers that are raw materials for other repeating units, a photopolymerization initiator or It can be produced by a method of copolymerization using a thermal polymerization initiator.

As the photopolymerization initiator used in the production of the polymer compound (A), radical polymerization initiators are preferred. -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 ketal, benzyl diethyl ketal, and diacetyl carbonyl compounds,
Anthraquinone or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, and sulfur compounds such as diphenyldisulfides and dithiocarbamates.

As the thermal polymerization initiator used in the production of the polymer compound (A), radical polymerization initiators are preferred, such as 2,2′-azobisisobutyronitrile and 2,2′-azobisisovaleronitrile. , 2,2′-azobis(2,4-dimethylvaleronitrile), 4,4′-azobis(4-cyanovaleric acid), 1,1′-azobis(cyclohexanecarbonitrile), 2,2′-azobis (2-methylpropane), and azo compounds such as 2,2′-azobis(2-methylpropionamidine) dihydrochloride,
ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide;
diacyl peroxides such as isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, and p-chlorobenzoyl peroxide;
Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di- dialkyl peroxides such as tert-butyl peroxide and tris(tert-butylperoxy)triazine,
peroxyketals such as 1,1-di-tert-butylperoxycyclohexane and 2,2-di(tert-butylperoxy)butane;
tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate , tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, and di-tert-butylperoxytrimethyladipate, and diisopropyl Peroxydicarbonate, di-sec-butylperoxydicarbonate, and tert-butylperoxyisopropylcarbonate.

In the production of the polymer compound (A), the charged molar ratio of the raw material monomers of the repeating unit represented by the formula (1) is 5 mol% or more and 100 mol% or less of all the monomers involved in the polymerization. is preferably 10 mol % or more and 100 mol % or less. By adjusting the charged molar ratio of the above monomers within this range, a crosslinked structure is sufficiently formed inside the cured product obtained by curing the composition of the present invention, and the solvent resistance is improved.

(Method for producing polymer compound (B))
The polymer compound (B) is produced, for example, by a method of polymerizing a monomer (polymerizable monomer), which is a raw material of the repeating unit represented by the above formula (2), using a photopolymerization initiator or a thermal polymerization initiator. can do.
When the polymer compound (B) has a repeating unit represented by formula (2) and at least one selected from the group consisting of repeating units represented by formula (4) and other repeating units, At least selected from the group consisting of a monomer that serves as a raw material for a repeating unit represented by formula (2), a monomer that serves as a raw material for a repeating unit that is represented by formula (4), and a monomer that serves as a raw material for another repeating unit It can be produced by a method of copolymerizing one monomer with a photopolymerization initiator or a thermal polymerization initiator.

In the production of the polymer compound (B), the charged molar ratio of the raw material monomers of the repeating unit represented by the formula (2) is preferably 5 mol% or more and 100 mol among all the monomers involved in the polymerization. % or less, more preferably 10 mol % or more and 100 mol % or less. By adjusting the charged molar ratio of the above monomers within this range, a crosslinked structure is sufficiently formed inside the cured product obtained by curing the composition of the present invention, and the solvent resistance is improved.

As the photopolymerization initiator or thermal polymerization initiator used in the production of the polymer compound (B), the same initiators as those used in the production of the polymer compound (A) can be used.

Cured Films of Compositions Cured films can be produced using the compositions of the present invention. The cured film is
A step of applying the already-described composition of the present invention, for example, to the surface of a substrate to be formed to form a coating layer;
It can be formed by a manufacturing method including a step of curing the coating layer.

The method for producing a cured film is, for example,
A step of adding an organic solvent to the composition of the present invention to obtain a coating liquid;
A step of applying the coating liquid to the surface of the substrate to form a coating layer;
The manufacturing method may include a step of curing the coating layer.

The organic solvent used in the step of obtaining the coating liquid is not particularly limited as long as it dissolves components such as the polymer compound and the cross-linking agent contained in the composition, and preferably has a boiling point of 100° C. to 100° C. at normal pressure. It is an organic solvent at 200°C.
Examples of suitable organic solvents include 2-heptanone, propylene glycol monomethyl ether acetate, cyclopentanone, and the like.
The coating liquid may contain a leveling agent, a surfactant, a curing catalyst, etc., if necessary.

The organic solvent contained in the coating liquid is preferably 30% by mass to 95% by mass with respect to the entire coating liquid.

In the step of forming a coating layer (hereinafter sometimes referred to as a coating step), a coating liquid is applied onto a substrate by a known coating method such as spin coating, die coating, screen printing, and inkjet. This can be done by forming

The step of curing the coating layer (hereinafter sometimes referred to as a curing step) may be a step of advancing a cross-linking reaction due to the reactive functional groups of the polymer compound contained in the coating layer. or by heating with a heater, an oven, or the like.
When the coating layer is heated, it is usually heated for 1 minute or more and 120 minutes or less, preferably 10 minutes or more and 60 minutes or less. The heating temperature of the coating film is preferably 80° C. or higher and 250° C. or lower, more preferably 100° C. or higher and 230° C. or lower, since the insulating layer to be formed has excellent crosslinkability and insulating properties.

A step of drying the coating layer (hereinafter sometimes referred to as a drying step) may be provided between the step of forming the coating layer and the step of curing the coating layer.
The purpose of the step of drying the coating layer is to remove the solvent in the coating layer formed on the substrate by the coating method. The drying step can be performed, for example, by heating with a heater, an oven, or the like.
When the coating layer is heated, it is usually heated for 1 minute or more and 120 minutes or less, and preferably 2 minutes or more and 60 minutes or less. The heating temperature is preferably 40° C. or higher and 250° C. or lower, more preferably 60° C. or higher and 230° C. or lower.

ELECTRONIC DEVICE An electronic device comprising the cured film described above will now be described. Since the composition of the present invention can be cured using a polymer compound that cures at a low temperature, a cured film using the composition of the present invention can be applied to various electronic devices such as organic thin film transistors, organic LEDs, and sensors. can be used.
An organic thin film transistor is suitable as an electronic device containing a cured film using the composition of the present invention. The organic thin film transistor preferably contains the cured film as a gate insulating layer of the organic thin film transistor.

In addition, since the "film obtained by curing the composition" of the present invention is excellent in insulating properties, sealing properties, adhesion properties, and solvent resistance, it can also be used as a protective layer such as an overcoat layer or an undercoat layer for organic thin-film transistors. can.
The organic thin film transistor 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, which is a film obtained by curing the composition of the present invention.
Organic thin film transistors to which the cured film of the present invention can be preferably applied are described below.

Organic Thin Film Transistor The organic thin film transistor includes the above cured film as a gate insulating layer.
The organic thin film transistor may be a bottom-gate top-contact type (first embodiment), a bottom-gate bottom-contact type (second embodiment), or a top-gate bottom-contact type (third embodiment). ).
Hereinafter, embodiments of an organic thin film transistor to which the composition of the present invention is preferably applied will be described with reference to the drawings.

FIG. 1 is a schematic diagram schematically showing the structure of a bottom-gate top-contact type organic thin film transistor according to the first embodiment.
As shown in FIG. 1, an organic thin film transistor 10 of the first embodiment includes a substrate 1, a gate electrode 2 provided so as to be in contact with the main surface of the substrate 1, and a substrate 1 covering the gate electrode 2. A gate insulating layer 3 provided, an organic semiconductor layer 4 provided so as to cover directly above the gate electrode 2 and being in contact with the gate insulating layer 3, and a channel provided so as to be in contact with the organic semiconductor layer 4. A source electrode 5 and a drain electrode 6 provided on the substrate 1 are separated from each other so that the region is interposed therebetween and the channel region overlaps the gate electrode 2 when viewed in the thickness direction of the substrate 1 (in a plan view). and an overcoat layer 7 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 .

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

FIG. 3 is a schematic diagram schematically showing the structure of a top-gate-bottom-contact organic thin-film transistor 10 according to the third embodiment.
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 on the substrate 1, and a source electrode 5 and a drain electrode 6 on the substrate 1. The formed organic semiconductor layer 4, the gate insulating layer 3 formed on the organic semiconductor layer 4, the gate electrode 2 formed on the gate insulating layer 3, the source electrode 5 and the drain electrode provided on the substrate 1. 6, an overcoat layer 7 covering the organic semiconductor layer 4, the gate insulating layer 3 and the gate electrode 2;

Method for Manufacturing Organic Thin Film Transistor A bottom-gate top-contact type organic thin film transistor 10 of the first embodiment has, for example, a gate electrode 2 formed on the main surface of a substrate 1 and a gate electrode 2 provided so as to cover the gate electrode 2. A gate insulating layer 3 is formed on the surface of a substrate 1, 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 in contact with the organic semiconductor layer 4, and, if necessary, For example, it can be manufactured by forming an 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 .

In the bottom-gate-bottom-contact organic thin-film transistor 10 of the second embodiment, for example, the gate electrode 2 is formed on the main surface of the substrate 1, and the gate electrode 2 is provided on the surface of the substrate 1 so as to cover the gate electrode 2. forming a gate insulating layer 3; forming a source electrode 5 and a drain electrode 6 on the gate insulating layer 3; and, if necessary, the gate electrode 2 provided on the substrate 1, the gate insulating layer 3, the organic semiconductor layer 4, the source electrode 5 and the drain It can be manufactured by forming an overcoat layer 7 so as to cover the electrode 6 .

In the top-gate-bottom-contact organic thin-film transistor 10 of the third embodiment, for example, the source electrode 5 and the drain electrode 6 are formed on the main surface of the substrate 1, and the organic semiconductor layer is formed so as to span the source electrode 5 and the drain electrode 6. 4 is formed, a gate insulating layer 3 is formed, a gate electrode 2 is formed, and, if necessary, a source electrode 5, a drain electrode 6, an organic semiconductor layer 4, a gate insulating layer 3 and a gate provided on the substrate 1 are formed. It can be manufactured by forming an overcoat layer 7 so as to cover the electrode 2 .

For the gate insulating layer 3, a film obtained by curing the composition of the present invention, which has already been described, can be used.

The contact angle of the gate insulating layer 3 with respect to pure water is determined by considering the amount of fluorine atoms, hydrophobic functional groups, and hydrophilic functional groups in 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 curing step (heating or baking) performed when forming the gate insulating layer 3 are performed in an oxygen-containing atmosphere, the hydrophilicity of the surface of the gate insulating layer 3 increases, and the inert gas If it is carried out in an atmosphere, the hydrophilicity of the surface of the gate insulating layer 3 is lowered. When heating is performed in an oxygen-containing atmosphere, the hydrophilicity of the surface of the gate insulating layer 3 increases as the temperature increases.

In particular, by adjusting the amount of fluorine atoms contained in the composition, 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 made a good interface. be able to. This can further improve the carrier mobility of the organic thin film transistor.

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

A self-assembled monolayer may be formed on the surface of the gate insulating layer 3 on the side of the organic semiconductor layer 4 . 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 mass % of an alkylchlorosilane compound or an alkylalkoxysilane compound in an organic solvent.

Examples of alkylchlorosilane compounds for forming a self-assembled monolayer include methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, decyltrichlorosilane, octadecyltrichlorosilane, and the like.
Alkylalkoxysilane compounds for forming a 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 may be composed of materials and methods commonly used in conventionally known organic thin film transistor manufacturing methods.

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 materials for the gate electrode 2, source electrode 5, and drain electrode 6 include chromium, gold, silver, aluminum, molybdenum, and the like. The gate electrode 2, the source electrode 5, and the drain electrode 6 can be formed by a known method such as a vapor deposition method, a sputtering method, a coating method such as an inkjet printing method, or the like.

As the organic semiconductor compound that is the material of the organic semiconductor layer 4, a π-conjugated polymer is widely used. p-phenylene vinylene) and the like can be used.

As the organic semiconductor compound which is the material of the organic semiconductor layer 4, a low-molecular-weight compound having solubility in an organic solvent can also 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, and carbon nanotubes. Specific examples of such low-molecular-weight compounds include 9,9-di-n-octylfluorene-2,7-di(ethylene boronate) and 5,5′-dibromo-2,2′- Condensates with biothiophene and the like can be mentioned.

The step of forming the organic semiconductor layer 4 includes, for example, adding a solvent or the like to the organic semiconductor compound to prepare a coating liquid for forming the organic semiconductor layer 4, applying the liquid, and drying the coating layer. conduct. In the present invention, the polymer compound that constitutes the gate insulating layer 3 has a phenyl moiety or a carbonyl moiety, and has affinity with the 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 can dissolve or disperse the organic semiconductor compound. As such a solvent, a solvent having a boiling point of 50° C. to 200° C. under normal pressure is preferable. Examples of such solvents include chloroform, toluene, anisole, 2-heptanone, xylene, propylene glycol monomethyl ether acetate, and the like. The coating liquid for forming the organic semiconductor layer 4 is applied to the substrate by a known coating method such as spin coating, die coating, screen printing, inkjet printing, etc., similarly to the coating liquid for forming the insulating layer 3 already described. 1 or on the gate insulating layer 3 .

The overcoat layer 7 (protective layer) can be formed in the same manner as in the step of forming the gate insulating layer 3 already described, using, for example, the composition of the present invention already described.
Also, an undercoat layer (not shown) can be formed in the same manner as the overcoat layer 7 .

By using the composition of the present invention, it is possible to obtain a composition that has good storage stability and cures at a low temperature. As a result, the step of forming the gate insulating layer, and thus the method of manufacturing the organic thin film transistor, can be carried out more simply. .

Use of Organic Thin-Film Transistor The organic thin-film transistor produced using the composition of the present invention can be used to produce a display member containing an organic thin-film transistor. Moreover, a display provided with a display member can be manufactured using the display member containing the organic thin film transistor.

Organic thin film transistors formed using the compositions of the present invention can also be used in OFET sensors. An 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 electrical signal and outputs it. is given a sensitive function or a selective function. OFET sensors include, for example, biosensors, gas sensors, ion sensors, and humidity sensors.

For example, a biosensor comprises an organic thin film transistor having the configuration as described above.
Organic thin film transistors have probes (sensitive regions) that specifically interact with target substances in the channel region and/or the gate insulating layer. When the concentration of the target substance changes, the electrical properties of the probe change, so that it can function as a biosensor.

Methods for detecting a target substance in a test sample include, for example, a method in which 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.

This method utilizes the specific affinity between substances or between functional groups, such as interaction of nucleic acid strands having complementary sequences, antigen-antibody reaction, enzyme-substrate reaction, receptor-ligand interaction, etc. Then, the target substance is captured by the probe on the solid phase carrier. Therefore, a substance or functional group that has a specific affinity for the target substance is selected as a probe.

The probe is immobilized on the surface of the solid-phase carrier by a method suitable for the selected probe type and solid-phase carrier type. It is also possible to synthesize probes on the surface of a solid phase carrier (for example, synthesize probes by nucleic acid extension reaction). In either case, the probe immobilized on the surface of the solid-phase carrier is brought into contact with the test sample and treated under appropriate conditions to form a probe-target substance complex on the surface of the solid-phase carrier. . The channel region and/or gate insulating layer of the organic thin film transistor itself may serve as probes.

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

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

Organic thin film transistors formed using the compositions of the present invention can also be used in the manufacture of pressure sensors. The pressure sensor comprises an organic thin film transistor having the configuration as described above. In this case, in the organic thin film transistor, the channel region and/or the gate insulating layer function as a pressure sensitive portion. When stress is applied to the pressure-sensitive portion, the electrical characteristics of the pressure-sensitive portion change, so that the pressure-sensitive portion can function as a pressure sensor.

When the channel region functions as a pressure-sensitive portion, the organic thin film transistor may further have an orientation layer in order to further improve the crystallinity of the organic semiconductor contained in the channel region. The alignment layer includes, for example, a monomolecular layer provided so as to be bonded to the gate insulating layer using a silane coupling agent such as hexamethyldisilazane.

An organic thin film transistor formed using the composition of the present invention can also be used to manufacture a conductivity modulation 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. The membrane containing the composition of (1) is provided with a sensitive function or a selective function for the input of the detection target. A conductivity-modulated sensor detects the input to be detected as a change in the conductivity of the composition of the invention. Examples of conductivity modulation sensors include biosensors, gas sensors, ion sensors, and humidity sensors.

Further, the organic thin film transistor formed using the composition of the present invention is an amplifier circuit containing an organic thin film transistor for amplifying output signals from various sensors such as biosensors, gas sensors, ion sensors, humidity sensors, and pressure sensors. It can also be used for the production of

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

In addition, the organic thin film transistor formed using the composition of the present invention is integrated with a plurality of various sensors such as biosensors, gas sensors, ion sensors, humidity sensors, and pressure sensors, and the output signals from each sensor are individually amplified. It can also be used in the manufacture of a sensor array with an amplifier circuit containing organic thin film transistors for the purpose of

The present invention will be described in more detail below with reference to examples. The invention is not limited to the examples described below.
In the examples, the storage stability was evaluated by visually observing the state after 2 months, 5 months, or 7 months under room temperature conditions after manufacturing the composition, and gelation of the composition was evaluated. When confirmed, the evaluation was terminated at that point.

(molecular weight analysis)
The number-average molecular weight and weight-average molecular weight of polymer compound C, which will be described later, were determined using gel permeation chromatography (GPC, manufactured by Waters, trade name: Alliance GPC 2000). Polymer compound C to be measured was dissolved in ortho-dichlorobenzene and injected into GPC. Ortho-dichlorobenzene was used as the mobile phase for GPC. As the column, "TSKgel GMHHR-H(S)HT (double connection, manufactured by Tosoh Corporation)" was used. A UV detector was used as the detector.

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

Synthesis Example 1 (Synthesis of polymer compound C)
A polymer compound C was synthesized according to the following scheme.
After replacing the gas in the reaction vessel with nitrogen gas, compound B-1 represented by the following formula B-1 (286.8 mg, 0.200 mmol), 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 a 3 mol/L potassium phosphate aqueous solution was added dropwise to the obtained reaction solution, and the mixture was refluxed for 3 hours. 24.4 mg of phenylboronic acid was added to the resulting reaction solution and refluxed for 1 hour. To the obtained 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 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 resulting toluene solution was added dropwise to acetone, a precipitate was obtained. The resulting precipitate was Soxhlet-washed using acetone as a solvent to obtain polymer compound C containing a repeating unit represented by the following formula. The obtained amount of polymer compound C was 244 mg, the polystyrene-equivalent number average molecular weight was 3.1×10 ⁴ , and the weight average molecular weight was 6.5×10 ⁴ .

Synthesis Example 2-1 (Synthesis of polymer compound (1))
Benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.61 g, 2-[bis (ethoxycarbonyl) methyl] carbonylamino]-ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name "Karenzu MOI-DEM") 1.51 g, 2,2 '-azobis (2-methylpropionitrile) 0.063 g, 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.44 g, put in a 50 mL pressure container (manufactured by ACE GLASS Co., Ltd.), bubbled with nitrogen gas, and then sealed. and a 70° C. oil bath for 18 hours to obtain a copolymer solution. Polymer compound (1) had a polystyrene-equivalent number-average molecular weight of 2.5×10 ⁴ and a weight-average molecular weight of 1.0×10 ⁵ .

Synthesis Example 2-2 (Synthesis of polymer compound (2))
4.19 g of styrene (manufactured by Junsei Chemical Co., Ltd.), 3.90 g of 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich), 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate ( Showa Denko Co., Ltd., trade name “Karenzu MOI-DEM”) 2.11 g, 2,2′-azobis(2-methylpropionitrile) 0.051 g, 2-heptanone (manufactured by Tokyo Kasei Co., Ltd.) 10.25 g, It was placed 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 15 hours to obtain a copolymer solution. Polymer compound (2) had a polystyrene-equivalent number-average molecular weight of 4.2×10 ⁴ and a weight-average molecular weight of 9.6×10 ⁴ .

Synthesis Example 2-3 (Synthesis of polymer compound (3))
2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 8.60 g, 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate (manufactured by Showa Denko, trade name "Karenzu MOI- DEM”) 1.55 g, 2,2′-azobis(2-methylpropionitrile) 0.051 g, and 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.16 g are placed in a 50 mL pressure container (manufactured by ACE GLASS). After bubbling with nitrogen gas, the flask was sealed and polymerized in an oil bath at 70° C. for 15 hours to obtain a copolymer solution. Polymer compound (3) had a polystyrene-equivalent number-average molecular weight of 3.6×10 ⁴ and a weight-average molecular weight of 7.5×10 ⁴ .

Synthesis Example 2-4 (Synthesis of polymer compound (4))
Styrene (manufactured by Junsei Chemical Co., Ltd.) 7.50 g, 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name "Karenzu MOI-DEM") 2.52 g, 2,2' - 0.050 g of azobis(2-methylpropionitrile) and 15.11 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Kasei Co., Ltd.) are placed in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, and then sealed. and polymerized in an oil bath at 70° C. for 16 hours to obtain a copolymer solution. Polymer compound (4) had a polystyrene-equivalent number-average molecular weight of 3.8×10 ⁴ and a weight-average molecular weight of 7.3×10 ⁴ .

Synthesis Example 2-5 (Synthesis of polymer compound (5))
Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 6.76 g, 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate (manufactured by Showa Denko, trade name "Karenzu MOI-DEM") 2.37 g, 2 , 2′-azobis(2-methylpropionitrile) 0.099 g, 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.52 g, put in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, It was sealed and polymerized in an oil bath at 70° C. for 18 hours to obtain a copolymer solution. Polymer compound (5) had a polystyrene-equivalent number-average molecular weight of 2.0×10 ⁴ and a weight-average molecular weight of 7.4×10 ⁴ .

Synthesis Example 2-6 (Synthesis of polymer compound (6))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 8.15 g, 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate (manufactured by Showa Denko, trade name "Karenzu MOI-DEM") 1.07 g, 2,2'-azobis(2-methylpropionitrile) 0.045 g, 2-heptanone (manufactured by Tokyo Kasei Co., Ltd.) 21.61 g, 50 mL pressure container (ACE GLASS) ), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70° C. for 18 hours to obtain a copolymer solution. Polymer compound (6) had a polystyrene-equivalent number-average molecular weight of 2.7×10 ⁴ and a weight-average molecular weight of 1.2×10 ⁵ .

Synthesis Example 2-7 (Synthesis of polymer compound (7))
2,2,2-trifluoroethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.81 g, 2-[bis(ethoxycarbonyl)methyl]carbonylamino]-ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name “Karenzu MOI-DEM” ) 1.42 g, 0.059 g of 2,2′-azobis(2-methylpropionitrile), and 19.34 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Kasei Co., Ltd.) are placed in a 50 mL pressure vessel (manufactured by ACE GLASS). After bubbling with nitrogen gas, the flask was sealed and polymerized in an oil bath at 70° C. for 18 hours to obtain a copolymer solution. Polymer compound (7) had a polystyrene-equivalent number-average molecular weight of 3.2×10 ⁴ and a weight-average molecular weight of 8.7×10 ⁴ .

Synthesis Example 2-8 (Synthesis of polymer compound (8))
Benzyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 8.25 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 1.00 g, 2,2'-azobis (2-methylpropionitrile) 0.068 g, 2-heptanone (Tokyo Kasei Co., Ltd.) 21.73 g was placed in a 50 mL pressure container (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 18 hours to obtain a copolymer solution. . Polymer compound (8) had a polystyrene-equivalent number-average molecular weight of 2.8×10 ⁴ and a weight-average molecular weight of 1.0×10 ⁵ .

Synthesis Example 2-9 (Synthesis of polymer compound (9))
4.69 g of styrene (manufactured by Junsei Chemical Co., Ltd.), 4.37 g of 2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich), 1.08 g of 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.), 2, 0.051 g of 2′-azobis(2-methylpropionitrile) and 10.19 g of 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 50 mL pressure vessel (manufactured by ACE GLASS), bubbled with nitrogen gas, and then sealed. and polymerized in an oil bath at 70° C. for 15 hours to obtain a copolymer solution. Polymer compound (9) had a polystyrene-equivalent number-average molecular weight of 5.0×10 ⁴ and a weight-average molecular weight of 1.1×10 ⁵ .

Synthesis Example 2-10 (Synthesis of polymer compound (10))
2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 9.26 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.76 g, 2,2′-azobis(2-methylpropionitrile) ) 0.050 g and 10.07 g of 2-heptanone (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 50 mL pressure-resistant container (manufactured by ACE GLASS Co., Ltd.), bubbled with nitrogen gas, and then sealed and placed in an oil bath at 70 ° C. for 15 hours. Polymerization was performed to obtain a copolymer solution. Polymer compound (10) had a polystyrene-equivalent number-average molecular weight of 3.9×10 ⁴ and a weight-average molecular weight of 7.4×10 ⁴ .

Synthesis Example 2-11 (Synthesis of polymer compound (11))
Styrene (manufactured by Junsei Chemical Co., Ltd.) 9.37 g, 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 1.30 g, 2,2′-azobis(2-methylpropionitrile) 0.053 g, propylene glycol monomethyl ether acetate (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 50 mL pressure container (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 16 hours to obtain a copolymer solution. Obtained. Polymer compound (11) had a polystyrene-equivalent number-average molecular weight of 3.3×10 ⁴ and a weight-average molecular weight of 6.2×10 ⁴ .

Synthesis Example 2-12 (Synthesis of polymer compound (12))
Styrene (manufactured by Junsei Chemical Co., Ltd.) 9.37 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 1.44 g, 2,2'-azobis (2-methylpropionitrile) 0.054 g, cyclopentanol (Tokyo Kasei (manufactured by ACE GLASS) was placed 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 a copolymer solution. Polymer compound (12) had a polystyrene-equivalent number-average molecular weight of 5.4×10 ⁴ and a weight-average molecular weight of 1.3×10 ⁵ .

Synthesis Example 2-13 (Synthesis of polymer compound (13))
Styrene (manufactured by Junsei Chemical Co., Ltd.) 12.19 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 1.87 g, 2,2'-azobis (2-methylpropionitrile) 0.070 g, propylene glycol monomethyl ether acetate ( Tokyo Kasei Co., Ltd.) 14.13 g is placed in a 50 mL pressure container (Ace Glass Co., Ltd.), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 16 hours to obtain a copolymer solution. rice field. Polymer compound (13) had a polystyrene-equivalent number-average molecular weight of 3.9×10 ⁴ and a weight-average molecular weight of 8.6×10 ⁴ .

Synthesis Example 2-14 (Synthesis of polymer compound (14))
Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 7.75 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Chemical Co., Ltd.) 1.24 g, 2,2'-azobis (2-methylpropionitrile) 0.113 g, 2-heptanone (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 50 mL pressure container (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 18 hours to obtain a copolymer solution. Obtained. The polymer compound (14) had a polystyrene-equivalent number-average molecular weight of 1.9×10 ⁴ and a weight-average molecular weight of 5.5×10 ⁴ .

Synthesis Example 2-15 (Synthesis of polymer compound (15))
2,3,4,5,6-pentafluorobenzyl methacrylate (manufactured by Synquest Laboratories) 8.62 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.52 g, 2,2′-azobis (2- 0.049 g of methylpropionitrile) and 21.44 g of 2-heptanone (manufactured by Tokyo Kasei Co., Ltd.) are placed in a 50 mL pressure-resistant container (manufactured by ACE GLASS), bubbled with nitrogen gas, then sealed, and an oil bath at 70 ° C. Polymerization was carried out for 18 hours to obtain a copolymer solution. Polymer compound (15) had a polystyrene-equivalent number-average molecular weight of 3.0×10 ⁴ and a weight-average molecular weight of 9.9×10 ⁴ .

Synthesis Example 2-16 (Synthesis of polymer compound (16))
Benzyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 8.41 g, 2-hydroxypropyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 0.76 g, 2,2'-azobis (2-methylpropionitrile) 0.070 g, 2-heptanone (Tokyo Kasei Co., Ltd.) was placed in a 50 mL pressure container (manufactured by ACE GLASS), bubbled with nitrogen gas, sealed, and polymerized in an oil bath at 70 ° C. for 18 hours to obtain a copolymer solution. . Polymer compound (16) had a polystyrene-equivalent number-average molecular weight of 2.3×10 ⁴ and a weight-average molecular weight of 9.7×10 ⁴ .

Synthesis Example 2-17 (Synthesis of polymer compound (17))
2,2,2-trifluoroethyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) 7.57 g, 4-hydroxybutyl acrylate (manufactured by Nippon Kasei Co., Ltd.) 0.72 g, 2,2′-azobis(2-methylpropionitrile) 0 .066 g and 19.49 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 50 mL pressure-resistant container (manufactured by ACE GLASS Co., Ltd.), bubbled with nitrogen gas, sealed, and placed in an oil bath at 70 ° C. for 18 hours. Polymerization was performed to obtain a copolymer solution. Polymer compound (17) had a polystyrene-equivalent number-average molecular weight of 2.2×10 ⁴ and a weight-average molecular weight of 6.9×10 ⁴ .

Example 1
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of cyclopentanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by synthesis example. 0.91 g of the 2-heptanone solution of the polymer compound (8) obtained in 2-8 was added and stirred to obtain a homogeneous solution. It did not gel even after being left at room temperature for 2 months.

Example 2
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of methanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by Synthesis Example 2-. 0.91 g of the 2-heptanone solution of the polymer compound (8) obtained in 8 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 2 months.

Example 3
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of ethoxyethanol are placed in a 5 mL sample bottle and stirred to form a homogeneous solution. 0.91 g of the 2-heptanone solution of the polymer compound (8) obtained in -8 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 2 months.

Comparative example 1
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of 2-heptanone were placed in a 5-mL sample bottle and stirred to form a uniform solution. 0.91 g of the 2-heptanone solution of the polymer compound (8) obtained in 2-8 was added and stirred to obtain a homogeneous solution. When left at room temperature for 3 days, it gelled.

Comparative example 2
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of diethyl malonate were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by synthesis example. 0.91 g of the 2-heptanone solution of the polymer compound (8) obtained in 2-8 was added and stirred to obtain a uniform solution. When left at room temperature for 3 days, it gelled.

Comparative example 3
1.00 g of the 2-heptanone solution of the polymer compound (1) obtained in Synthesis Example 2-1 and 0.38 g of ethylene glycol were placed in a 5 mL sample bottle and stirred. When 0.91 g of a 2-heptanone solution of molecular compound (8) was added and stirred, a homogeneous solution was not obtained.

Example 4
1.00 g of the 2-heptanone solution of the polymer compound (2) obtained in Synthesis Example 2-2 and 0.38 g of methanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by Synthesis Example 2-. 0.88 g of the 2-heptanone solution of the polymer compound (9) obtained in 9 was added and stirred to obtain a homogeneous solution. It did not gel even after being left at room temperature for 5 months.

Comparative example 4
1.00 g of the 2-heptanone solution of the polymer compound (2) obtained in Synthesis Example 2-2 and 0.38 g of PGMEA were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by Synthesis Example 2-9. 0.88 g of the 2-heptanone solution of the polymer compound (9) obtained in 1. was added and stirred to obtain a uniform solution. When left at room temperature for 3 days, it gelled.

Example 5
1.50 g of the 2-heptanone solution of the polymer compound (3) obtained in Synthesis Example 2-3 and 0.92 g of methanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, followed by Synthesis Example 2-. 0.69 g of the 2-heptanone solution of the polymer compound (10) obtained in 10 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 5 months.

Comparative example 5
1.00 g of the 2-heptanone solution of the polymer compound (3) obtained in Synthesis Example 2-3 and 0.61 g of toluene were placed in a 5 mL sample bottle, stirred to form a uniform solution, and then Synthesis Example 2- 0.69 g of the 2-heptanone solution of the polymer compound (10) obtained in 10 was added and stirred to obtain a uniform solution. When left at room temperature for 3 days, it gelled.

Example 6
1.50 g of the PGMEA solution of the polymer compound (4) obtained in Synthesis Example 2-4 and 0.48 g of cyclopentanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, and then Synthesis Example 2- 0.80 g of the PGMEA solution of the polymer compound (11) obtained in 11 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 7 months.

Comparative example 6
1.50 g of the PGMEA solution of the polymer compound (4) obtained in Synthesis Example 2-4 and 0.48 g of PGMEA were placed in a 5 mL sample bottle and stirred to form a uniform solution, which was obtained in Synthesis Example 2-11. 0.80 g of the PGMEA solution of polymer compound (11) was added and stirred to obtain a homogeneous solution. When left at room temperature for 4 days, gelation occurred.

Example 7
1.50 g of the PGMEA solution of the polymer compound (4) obtained in Synthesis Example 2-4 and 0.91 g of cyclopentanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, and then Synthesis Example 2- 1.08 g of the cyclopentanol solution of the polymer compound (12) obtained in 12 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 7 months.

Example 8
1.50 g of the PGMEA solution of the polymer compound (4) obtained in Synthesis Example 2-4 and 0.91 g of cyclopentanol were placed in a 5 mL sample bottle and stirred to form a uniform solution, and then Synthesis Example 2- 1.08 g of the PGMEA solution of the polymer compound (13) obtained in 13 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 7 months.

Comparative example 7
1.50 g of the PGMEA solution of the polymer compound (4) obtained in Synthesis Example 2-4 and 0.91 g of PGMEA were placed in a 5 mL sample bottle and stirred to form a uniform solution, which was obtained in Synthesis Example 2-13. 1.08 g of the PGMEA solution of polymer compound (13) was added and stirred to obtain a uniform solution. When left at room temperature for 4 days, it gelled.

Example 9
0.71 g of the 2-heptanone solution of the polymer compound (5) obtained in Synthesis Example 2-5 and 0.42 g of cyclopentanol were placed in a 5 mL sample bottle, stirred to form a uniform solution, and then prepared in Synthesis Example. 1.38 g of the 2-heptanone solution of the polymer compound (14) obtained in 2-14 was added and stirred to obtain a uniform solution. It did not gel even after being left at room temperature for 2 months.

Comparative example 8
0.71 g of the 2-heptanone solution of the polymer compound (5) obtained in Synthesis Example 2-5 and 0.42 g of 2-heptanone were placed in a 5-mL sample bottle and stirred to form a uniform solution. 1.38 g of the 2-heptanone solution of the polymer compound (14) obtained in 2-14 was added and stirred to obtain a uniform solution. When left at room temperature for 4 days, it gelled.

Example 10
2.00 g of the 2-heptanone solution of the polymer compound (6) obtained in Synthesis Example 2-6 and 0.78 g of cyclopentanol were placed in a 10 mL sample bottle and stirred to form a uniform solution, followed by synthesis example. 1.87 g of the 2-heptanone solution of the polymer compound (15) obtained in 2-15 was added and stirred to obtain a homogeneous solution. It did not gel even after being left at room temperature for 2 months.

Comparative example 9
1.00 g of the 2-heptanone solution of the polymer compound (6) obtained in Synthesis Example 2-6 and 0.38 g of 2-heptanone were placed in a 5-mL sample bottle and stirred to form a uniform solution. 0.94 g of the 2-heptanone solution of the polymer compound (15) obtained in 2-15 was added and stirred to obtain a uniform solution. When left at room temperature for 8 days, it gelled.

Example 11
1.00 g of the 2-heptanone solution of the polymer compound (5) obtained in Synthesis Example 2-5 and 0.38 g of benzyl alcohol were placed in a 5 mL sample bottle and stirred to form a homogeneous solution. 0.91 g of the 2-heptanone solution of the polymer compound (16) obtained in (16) was added and dissolved by stirring to obtain a uniform solution. It did not gel even after being left at room temperature for 2 months.

Comparative example 10
1.00 g of the 2-heptanone solution of the polymer compound (5) obtained in Synthesis Example 2-5 and 0.38 g of 2-heptanone were placed in a 5-mL sample bottle and stirred to form a uniform solution. 0.91 g of the 2-heptanone solution of the polymer compound (16) obtained in 2-16 was added and stirred to obtain a homogeneous solution. When left at room temperature for 7 days, it gelled.

Example 12
1.00 g of the 2-heptanone solution of the polymer compound (7) obtained in Synthesis Example 2-7 and 0.95 g of cyclopentanol were placed in a 5-mL sample bottle and stirred to form a homogeneous solution. 0.91 g of the 2-heptanone solution of the polymer compound (17) obtained in 2-17 was added and stirred to obtain a homogeneous solution. It did not gel even after being left at room temperature for 2 months.

Comparative example 11
1.00 g of the 2-heptanone solution of the polymer compound (7) obtained in Synthesis Example 2-7 and 0.95 g of 2-heptanone were placed in a 5-mL sample bottle and stirred to form a uniform solution. 0.91 g of the 2-heptanone solution of the polymer compound (17) obtained in 2-17 was added and stirred to obtain a uniform solution. When left at room temperature for 3 days, it gelled.

Example 13 (Production and Evaluation of Insulating Layer)
The solution obtained in Example 5 was spin-coated onto a glass substrate with a chromium electrode. Then, it was dried on a hot plate at 130° C. for 30 minutes to obtain an insulating layer with a film thickness of 600 nm.

An MIM (Metal Insulator Metal) element was produced by forming an aluminum electrode on the obtained insulating layer by vapor deposition using a metal mask.
By evaluating the electrical properties of the MIN element, the composition for an insulating layer was evaluated.

The dielectric strength of the fabricated MIM element was measured using a vacuum prober (manufactured by Nagase Electronic Equipments Service Co., Ltd., BCT22MDC-5-HT-SCU;). Here, the withstand voltage was evaluated by applying an electric field between the electrodes and measuring the electrolytic strength at which the leak current was 1×10 ⁻⁹ A/cm ² .
The value of electric field strength at which the leak current is 1×10 ⁻⁹ A/cm ² was >3.0 MV/cm.

Example 14 (Production and Evaluation of Organic Thin Film Transistor (1))
Using the solution obtained in Example 5, a top gate bottom contact type organic thin film transistor (1) was manufactured.

First, the glass substrate was irradiated with ozone UV, then washed with an alkaline cleaning liquid, and rinsed with pure water.
Next, a source electrode and a drain electrode were formed by laminating chromium and gold in this order from the substrate side on a glass substrate by a sputtering method and patterning by photolithography. At this time, the source electrode and the drain electrode had a channel length of 10 μm and a channel width of 2 mm. Thereafter, the surface of the electrode (particularly gold) formed on the glass substrate was modified by immersing the glass substrate in an isopropyl alcohol diluted solution of perfluorobenzenethiol for 2 minutes.

Subsequently, a 0.5% by mass toluene solution of the polymer compound C obtained in Synthesis Example 1 was spin-coated on the source electrode and drain electrode sides, and heat-treated at 120° C. for 30 minutes using a hot plate, An organic semiconductor layer was formed.

On this organic semiconductor layer, the solution obtained in Example 5 was applied by a spin coating method, and the formed coating layer was heat-treated at 130 ° C. for 30 minutes to obtain a cured film in which the coating layer was cured. A gate insulating layer was formed. The thickness of the formed gate insulating layer was 991 nm.

Further, an aluminum film was formed on the gate insulating layer by a vapor deposition method to form a gate electrode, thereby obtaining an organic thin film transistor (1).

The obtained organic thin film transistor (1) was evaluated.
Specifically, using a vacuum prober (BCT22MDC-5-HT-SCU; manufactured by Nagase Electronic Equipments Service Co., Ltd.), a voltage is applied to the gate electrode of the organic thin film transistor (1) to set the gate voltage Vg. The carrier mobility was measured under the conditions of changing the voltage from 20V to -40V and changing the source-drain voltage Vsd from 0V to -40V.
The carrier mobility of the organic thin film transistor (1) was 0.41 cm ² /Vs.

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 (5)

a polymer compound (A) having a repeating unit represented by the following formula (1);
a polymer compound (B) having a repeating unit represented by the following formula (2);
A composition containing a compound represented by the following formula (3).

(1)
(In formula (1),
R ¹ represents a hydrogen atom or a methyl group , and R ² and R ³ represent a hydrogen atom .
R ⁴ and R ⁵ may be different from each other and represent a methyl group or an ethyl group .
Ra represents ^an ethylene group .
X represents an oxygen atom .
l represents an integer of 1 ;
* represents a binding position. )

(2)
(In formula (2),
^R6 represents a hydrogen atom or a methyl group , and ^R7 and ^R8 represent a hydrogen atom .
R ^b represents a group represented by -COO- .
R ^c represents an ethylene group, n-propylene group, isopropylene group, or n-butylene group .
m represents an integer of 1 ;
* represents a binding position. )

(3)
(In formula (3),
R ⁹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a group represented by the following formula (6) having 2 to 20 carbon atoms. The hydrogen atom in the alkyl group, cycloalkyl group, or group represented by the following formula (6) is a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 3 carbon atoms. It may be substituted with a cycloalkoxy group having up to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a fluorine atom. )

(6)
(In formula (6),
R ¹⁵ represents a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms,
R ¹⁶ represents a monovalent linear aliphatic hydrocarbon group having 1 to 19 carbon atoms,
q represents an integer from 1 to 19;
However, R ¹⁵ , R ¹⁶ and q are adjusted so that the total number of carbon atoms is 2-20. ) At least one polymer compound selected from the group consisting of the polymer compound (A) and the polymer compound (B) is a polymer compound further comprising a repeating unit represented by the following formula (4). A composition according to claim 1 .

(4)
(In formula (4),
R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ and R ¹² represent a hydrogen atom .
^R13 represents a fluorine atom .
R ^d represents a divalent organic group having 1 to 20 carbon atoms or a group represented by -COO- .
n 1 represents an integer from 0 to 5;
n2 represents an integer from 0 to 2 ;
When there are multiple Rd ^'s , they are different from each other.
* represents a binding position. ) The composition according to claim 1 or 2, wherein the compound represented by the formula (3) contained in the composition is 1% by mass or more and 90% by mass or less. A composition for an insulating layer of an electronic device comprising the composition according to any one of claims 1 to 3 . A composition for an insulating layer of an organic thin film transistor, comprising the composition according to any one of claims 1 to 3 .

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