JP2014047278A - Polymer compound, and insulating layer material including the polymer compound - Google Patents

Abstract

【選択図】なしProvided is a polymer compound capable of producing an insulating layer capable of forming a lyophilic solution and a liquid repellent pattern without containing a photocatalyst.
A polymer compound containing a repeating unit represented by formula (1).

[Selection figure] None

Description

  The present invention relates to a polymer compound and an insulating layer material containing the polymer compound.

  In recent years, various studies have been made on a method for manufacturing an organic thin film transistor, and in particular, studies have been made on forming a wiring pattern of a circuit board and a pattern of an organic semiconductor layer by an inkjet method.

  In order to suppress the spread and separation of droplets landed on a substrate or the like by an ink jet method and form a desired wiring pattern or organic semiconductor layer pattern, a liquid material is applied to a region outside the pattern forming region. A method for imparting liquid repellency (water repellency), a method for modifying the substrate surface so that the pattern formation region has lyophilicity (hydrophilicity) with the liquid material, and a pattern formation region near the boundary A method has been proposed in which a bank-like bank that suppresses the outflow of liquid material is formed, and a wiring pattern or the like is formed by ejecting liquid droplets into a pattern formation region.

  However, with the high integration of circuit boards, miniaturization of wiring patterns and organic semiconductor layer patterns is required, and it is difficult to form fine wiring patterns and the like by the above method.

  As a method for forming a fine pattern, for example, a photocatalyst-containing layer that is a water-repellent insulating layer is formed on a substrate, and the photocatalyst-containing layer is exposed through a mask to hydrophilize only the exposed portion. A method for forming various functional layers on a patterned pattern is disclosed (Patent Document 1).

JP-A-11-344804

  However, since the organic thin film transistor formed using the pattern forming method includes a layer containing a photocatalyst such as a metal oxide, there is a problem that the characteristics of the organic thin film transistor are deteriorated by the photocatalyst.

  The objective of this invention is providing the high molecular compound which can manufacture the insulating layer which can form a lyophilic and liquid repellent pattern, without containing a photocatalyst.

（１）
［式中、Ｒ^１は、水素原子又はメチル基を表す。Ｒ及びＲ^２は、それぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表す。Ｒ^ｆは、フッ素原子又はフッ素原子を有する炭素数１〜２０の一価の有機基を表す。Ａ^１は、二価の基を表す。ｎは、１〜４の整数を表す。Ｒが複数個ある場合、それらは同一であっても相異なってもよい。Ｒ^ｆが複数個ある場合、それらは同一であっても相異なってもよい。ａは、０又は１の整数を表す。］ That is, the present invention first provides a polymer compound containing a repeating unit represented by the formula (1).

(1)
[Wherein, R ¹ represents a hydrogen atom or a methyl group. R and R ² each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^f represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. A ¹ represents a divalent group. n represents an integer of 1 to 4. When there are a plurality of R, they may be the same or different. When there are a plurality of ^Rf , they may be the same or different. a represents an integer of 0 or 1. ]

The present invention secondly provides the polymer compound further comprising at least one repeating unit selected from the group consisting of a repeating unit containing a cyclic ether structure and a repeating unit containing the following first functional group. To do.

First functional group: a functional group capable of generating a second functional group capable of reacting with active hydrogen by the irradiation of electromagnetic waves or the action of heat.

（２）
［式中、Ｒ^３は、水素原子又はメチル基を表す。Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表す。Ｒ^ａは、二価の基を表す。ｔは、０又は１の整数を表す。］

（３）
［式中、Ｒ^７は、水素原子又はメチル基を表す。Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、及びＲ^１２は、それぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表す。Ｒ^ｄは、二価の基を表す。ｗは、０又は１の整数を表す。］ Thirdly, the present invention provides the polymer compound wherein the repeating unit containing a cyclic ether structure is a repeating unit represented by the formula (2) or a repeating unit represented by the formula (3).

(2)
[Wherein R ³ represents a hydrogen atom or a methyl group. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^a represents a divalent group. t represents an integer of 0 or 1. ]

(3)
[Wherein, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^d represents a divalent group. w represents an integer of 0 or 1. ]

  Fourthly, the present invention provides the polymer compound, wherein the first functional group is an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent.

（４）
［式中、Ｘ^ａは、酸素原子又は硫黄原子を表し、Ｒ^１５及びＲ^１６は、それぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表す。］ Fifthly, the present invention provides the polymer compound wherein the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are groups represented by the formula (4).

(4)
[Wherein, X ^a represents an oxygen atom or a sulfur atom, and R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]

（５）
［式中、Ｘ^ｂは、酸素原子又は硫黄原子を表し、Ｒ^１７、Ｒ^１８、及びＲ^１９は、それぞれ独立に、水素原子又は炭素数１〜２０の一価の有機基を表す。］ Sixthly, the present invention provides the polymer compound, wherein the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are groups represented by the formula (5).

(5)
[Wherein, X ^b represents an oxygen atom or a sulfur atom, and R ¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]

（６）
［式中、Ｒ^１３は、水素原子又はメチル基を表す。Ｒ^ｂは、二価の基を表す。Ｒ^１４は、酸により脱離しうる有機基を表す。Ｒ’は、水素原子又は炭素数１〜２０の一価の有機基を表す。Ａ^２は、−Ｏ−又は−ＣＯＯ−を表す。ｕは、０又は１の整数を表し、ｍは、１〜５の整数を表す。Ａ^２−Ｒ^１４が複数個ある場合、それらは同一であっても相異なってもよい。Ｒ’が複数個ある場合、それらは同一であっても相異なってもよい。］ Seventhly, this invention provides the said high molecular compound containing the repeating unit represented by Formula (6) further.

(6)
[Wherein, R ¹³ represents a hydrogen atom or a methyl group. R ^b represents a divalent group. R ¹⁴ represents an organic group that can be eliminated by an acid. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A ² represents —O— or —COO—. u represents an integer of 0 or 1, and m represents an integer of 1 to 5. When there are a plurality of A ² —R ¹⁴ , they may be the same or different. When there are a plurality of R ′, they may be the same or different. ]

（７）
［式中、Ｒ^１、Ｒは、水素原子又は炭素数１〜２０の一価の有機基を表す。Ｒ^ｆは、フッ素原子又はフッ素原子を有する炭素数１〜２０の一価の有機基を表す。Ａ^１は、二価の基を表す。Ｒ^２は、水素原子又はメチル基を表す。ａは、０または１を表す。Ｒが複数個ある場合、それらは同一でも相異なっていてもよい。Ｒ^ｆが複数個ある場合、それらは同一でも相異なっていてもよい。ｎは、１から４の整数を表す。］ Eighth, the present invention provides a compound represented by formula (7).

(7)
[Wherein R ¹ and R each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^f represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. A ¹ represents a divalent group. R ² represents a hydrogen atom or a methyl group. a represents 0 or 1; When there are a plurality of R, they may be the same or different. When there are a plurality of ^Rf , they may be the same or different. n represents an integer of 1 to 4. ]

  Ninthly, this invention provides the insulating-layer material containing the said high molecular compound.

Tenth aspect of the present invention is a step of applying a liquid containing the insulating layer material to a base material to form a coating layer on the base material;
Applying heat to the coating layer and curing; and irradiating a part of the cured coating layer through a mask with an electromagnetic wave or an electron beam to form a lyophilic and liquid-repellent pattern;
A method of forming an insulating layer including the above is provided.

  Eleventhly, the present invention provides a method for forming the insulating layer, wherein the electromagnetic wave is ultraviolet light.

  12thly this invention provides the organic thin-film transistor which has an insulating layer formed using the said insulating-layer material.

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

  14thly this invention provides the display containing the said member for a display.

  Since the polymer compound of the present invention can produce an insulating layer capable of forming a lyophilic solution and a liquid repellent pattern without containing a photocatalyst, the present invention is extremely useful.

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

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

<Polymer compound>
The polymer compound of the present invention includes a repeating unit represented by the formula (1).

In formula (1), R ¹ represents a hydrogen atom or a methyl group. In some one aspect, R ¹ is methyl group.

In the formula (1), R and ^{R 2} represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R and R ² include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and carbon. A cyclic hydrocarbon group having 3 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms, preferably carbon. C1-C6 linear hydrocarbon group, C3-C6 branched hydrocarbon group, C3-C6 cyclic hydrocarbon group, C1-C6 alkoxy group, C6-C20 An aromatic hydrocarbon group, and an aryloxy group having 6 to 20 carbon atoms.
The monovalent organic group having 1 to 20 carbon atoms represented by R and R ² does not contain a fluorine atom.

  The alkoxy group may be linear, branched, or cyclic.

  In the aromatic hydrocarbon group having 6 to 20 carbon atoms, a hydrogen atom in the group may be substituted with a chlorine atom, a bromine atom, an iodine atom or the like, and may contain an alkyl group.

  An aryloxy group means a group in which an oxygen atom is bonded to an aromatic carbocycle. In the aryloxy group, a hydrogen atom in the group may be substituted with an alkyl group, a chlorine atom, a bromine atom, an iodine atom or the like.

Specific examples of the monovalent organic group having 1 to 20 carbon atoms 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, cyclohexylinyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethyl Phenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, ethenylnaphthyl group, methylanthryl group, ethylanthryl group, chlorophenyl group, bromophenyl group, methoxy group, Ethoxy , Propoxy group, butyloxy group, pentyloxy group, hexyloxy group, isopropoxy group, isobutyloxy group, tert-butyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclopentynyloxy Group, cyclohexynyloxy group, phenoxy group, naphthoxy group, anthryloxy group, methylphenoxy group, dimethylphenoxy group, trimethylphenoxy group, ethylphenoxy group, diethylphenoxy group, triethylphenoxy group, propylphenoxy group, butylphenoxy group, Examples include methylnaphthoxy group, dimethylnaphthoxy group, trimethylnaphthoxy group, methylanthryloxy group, ethylanthryloxy group, chlorophenoxy group, and bromophenoxy group. It is.
As a C1-C20 monovalent organic group, an alkyl group and an alkoxy group are preferable.
In some one aspect, R is methoxy, R ² is a methyl group.

In formula (1), A ¹ represents a divalent group. The divalent group is preferably a divalent group having a structure that does not exhibit reactivity under environmental conditions for crosslinking the insulating layer material of the present invention. Examples of the divalent group include a divalent organic group having 1 to 20 carbon atoms, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NHCOO-, -OCONH- and a group in which these groups are combined may be mentioned.
In some one form, A ¹ is a divalent organic group having 1 to 20 carbon atoms.

The divalent organic group having 1 to 20 carbon atoms represented by A ¹ may be linear, branched or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Also good. Examples of the divalent organic group having 1 to 20 carbon atoms include a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms and a divalent branched aliphatic hydrocarbon group having 3 to 20 carbon atoms. Group, a C3-C20 bivalent cyclic hydrocarbon group, and the C6-C20 bivalent aromatic hydrocarbon group which may be substituted are mentioned. Among them, a divalent linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms. And a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted with and.

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

  Examples of the optionally substituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, ethylenephenylene group, diethylenephenylene group, Examples include triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and ethylanthrylene group. It is done.

  In formula (1), a is an integer of 0 or 1. In one certain form, a is 0.

In formula (1), ^Rf represents a C1-C20 monovalent organic group which has a fluorine atom or a fluorine atom. Examples of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom include, for example, an alkyl group having 1 to 20 carbon atoms substituted with a fluorine atom, an alkoxy group having 1 to 20 carbon atoms substituted with a fluorine atom, C6-C20 aromatic hydrocarbon group substituted with a fluorine atom, C6-C20 aryloxy group substituted with a fluorine atom, and C7-C20 arylalkyloxy substituted with a fluorine atom Groups.

Examples of the C1-C20 alkyl group substituted with a fluorine atom include a trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, Perfluoroheptyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,3-trifluoropropyl group, And 3,3,4,4,4-pentafluorobutyl group. Examples of the C1-C20 alkoxy group substituted with a fluorine atom include a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3,3-pentafluoropropoxy group, Perfluorobutyloxy group, perfluoropentyloxy group, perfluoroheptyloxy group, 2,2,3,3,3-pentafluoropropyloxy group, 2,2,3,3,4,4,4-heptafluoro Examples thereof include a butyloxy group, a 3,3,3-trifluoropropyloxy group, and a 3,3,4,4,4-pentafluorobutyloxy group. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a fluorine atom include 2,3,4,5,6-pentafluorophenyl group, trifluoromethylphenyl group, 2,3,4,5. , 6-pentafluorophenylmethyl group, trifluoromethylphenylmethyl group, 2- (2,3,4,5,6-pentafluorophenyl) ethyl group, and 2- (trifluoromethylphenyl) ethyl group It is done. Examples of the aryloxy group having 6 to 20 carbon atoms substituted with a fluorine atom include a 2,3,4,5,6-pentafluorophenoxy group and a trifluoromethylphenoxy group. Examples of the arylalkyloxy group having 7 to 20 carbon atoms substituted with a fluorine atom include 2,3,4,5,6-pentafluorophenylmethoxy group, trifluoromethylphenylmethoxy group, 2- (2,3 , 4,5,6-pentafluorophenyl) ethoxy group and 2- (trifluoromethylphenyl) ethoxy group.
In one certain form, ^Rf is a 2,3,4,5,6-pentafluorophenylmethoxy group.

  In formula (1), n represents an integer of 1 to 4. In one certain form, n is 1.

The polymer compound of the present invention preferably further contains at least one repeating unit selected from the group consisting of a repeating unit containing a cyclic ether structure and a repeating unit containing the following first functional group.

First functional group: a functional group capable of generating a second functional group capable of reacting with active hydrogen by the irradiation of electromagnetic waves or the action of heat.

Examples of the repeating unit containing a cyclic ether structure include a repeating unit represented by the formula (2) and a repeating unit represented by the formula (3).

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

In formula (2), R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ are the monovalent monovalent organic groups having 1 to 20 carbon atoms represented by R and R ² described above. The definition and specific examples of the organic group are the same.
In one certain form, R < ⁴ >, R < ⁵ > and R < ⁶ > are hydrogen atoms.

In formula (2), R ^a represents a divalent group. The definition and specific examples of the divalent group represented by R ^a are the same as the definition and specific examples of the divalent group represented by A ¹ in the introduction.
R ^a is preferably —COO— or —OCO—.

  In formula (2), t represents an integer of 0 or 1. In one certain form, t is 1.

In formula (3), R ⁷ represents a hydrogen atom or a methyl group. In some one aspect, R ⁷ is a methyl group.

In Formula (3), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are 1 carbon atoms represented by R and R ² described above. The definition and specific examples of ˜20 monovalent organic groups are the same.
In one certain form, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R <^11> , and R < ¹² > are hydrogen atoms.

In formula (3), R ^d represents a divalent group. The definition and specific examples of the divalent group represented by R ^d are the same as the definition and specific examples of the divalent group represented by A ¹ in the introduction.
R ^d is preferably —COO— or —OCO—.

  In formula (3), w represents an integer of 0 or 1. In one certain form, w is 1.

  The polymer compound of the present invention may have a repeating unit containing the first functional group. As the first functional group, an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent are preferable.

  An isocyanate group blocked with a blocking agent can be produced by reacting an isocyanate group with a blocking agent having only one active hydrogen capable of reacting with the isocyanate group in one molecule.

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

  The blocking agent preferably dissociates at a temperature of 170 ° C. or lower after reacting with an isocyanato group or an isothiocyanato group. Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, urea compounds, and oxime compounds. , Amine compounds, imine compounds, bisulfites, pyridine compounds and pyrazole compounds. A blocking agent may be used individually and may be used in mixture of 2 or more types. Preferable blocking agents include oxime compounds and pyrazole compounds.

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

  Examples of the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent that may be used in the present invention include a group represented by the formula (4) and a group represented by the formula (5). Is preferred.

In the formula (4) and (5), ^{X a} represents an oxygen atom or a sulfur atom, ^{X b} represents an oxygen atom or a sulfur ^{atom, R 15, R 16, R} 17, R 18, and ^{R 19} Each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ are 1 carbon atoms represented by the aforementioned R and R ^2. The definition and specific examples of ˜20 monovalent organic groups are the same.
The monovalent organic group having 1 to 20 carbon atoms represented by R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ is preferably an alkyl group.

In some one ^{aspect, R 15} is a methyl ^{group, R 19} is ethyl ^group, R ^{17, R 18,} and ^{R 19} is a hydrogen atom.

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

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

  The first functional group is preferably an isocyanato group blocked with a blocking agent.

The first functional group does not react with active hydrogen. However, when the first functional group is irradiated with electromagnetic waves or heat is applied, a second functional group is generated, and the second functional group reacts with active hydrogen. To do. That is, the first functional group is deprotected by the irradiation of electromagnetic waves or the action of heat to generate a second functional group that reacts with active hydrogen.
In the present specification, active hydrogen refers to a hydrogen atom bonded to an atom other than a carbon atom such as an oxygen atom, a nitrogen atom and a sulfur atom.

  The second functional group is protected (blocked) until an electromagnetic wave is applied or heat is applied in the insulating layer forming step, and is present in the insulating layer material in the form of the first functional group. To do. As a result, the storage stability of the insulating layer material is improved.

  The polymer compound of the present invention preferably further contains a repeating unit represented by the formula (6).

In formula (6), R ¹³ represents a hydrogen atom or a methyl group. In some one aspect, R ¹³ is a methyl group.

In Formula (6), R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The definitions and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ^′ are the definitions and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R and R ² described above. Is the same.

In the formula (6), R ¹⁴ represents an organic group that can be removed by an acid. Examples of the organic group that can be eliminated by an acid include a hydrocarbon group having 4 to 20 carbon atoms having a branched structure or a cyclic hydrocarbon structure, an optionally substituted hydrocarbonyl group, and an optionally substituted hydropyranyl group. Can be mentioned.

Examples of the hydrocarbon group having 4 to 20 carbon atoms having a branched structure include a tert-butyl group, a 2,3-dimethyl-2-butyl group, and a 2,3,3-trimethyl-2-butyl group. It is done.
Examples of the hydrocarbon group having 4 to 20 carbon atoms having a cyclic hydrocarbon structure include 2-cyclopropyl-2-propyl group, 1-methyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1- Examples thereof include a methyl-1-cycloheptanyl group, a 2-methyl-2-adamantyl group, and a 2-adamantyl-2-propyl group. Examples of the substituent that the hydrofuranyl group and the hydropyranyl group may have include a hydroxy group, an alkoxy group, and an alkyl group.
The hydrofuranyl group means a group obtained by removing one hydrogen atom from dihydrofuran or tetrahydrofuran, and examples of the optionally substituted hydrofuranyl group include a tetrahydrofuranyl group.
The hydropyranyl group means a group obtained by removing one hydrogen atom from dihydropyran or tetrahydropyran. Examples of the hydropyranyl group which may be substituted include a tetrahydropyranyl group and a 4-methoxytetrahydropyranyl group. It is done.

In Formula (6), A ² represents —O— or —COO—. In one certain form, it is -O-.

  In formula (6), m represents an integer of 1 to 5. In one certain form, m is 1.

  The polymer compound (A) containing the repeating unit represented by the formula (1) is prepared by, for example, using a photopolymerization initiator or a thermal polymerization initiator as a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1). It can manufacture by the method of using and polymerizing.

  As a polymerizable monomer used as the raw material of the repeating unit represented by Formula (1), the compound represented by Formula (7) is mentioned, for example. Examples of the compound represented by the formula (7) include α-methyl- [5-methoxy-2-nitro-4- (2 ′, 3 ′, 4 ′, 5 ′, 6′-pentafluorobenzyl) oxy. Benzyl acrylate and [alpha] -methyl- [5-methoxy-2-nitro-4- (2 ', 3', 4 ', 5', 6'-pentafluorobenzyl) oxy] benzyl methacrylate.

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

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

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

  A polymer comprising a repeating unit represented by formula (1) and at least one repeating unit selected from the group consisting of a repeating unit containing a cyclic ether structure and a repeating unit containing the following first functional group Compound (A-1) includes, for example, a polymerizable monomer that is a raw material of the repeating unit represented by formula (1), a polymerizable monomer that is a raw material of the repeating unit containing a cyclic ether structure, and the first functional group. A method similar to the production of the polymer compound (A) using a polymerizable monomer mixture containing at least one polymerizable monomer selected from the group consisting of a polymerizable monomer which is a raw material of a repeating unit containing a group Can be manufactured. As a polymerizable monomer that is a raw material of a repeating unit containing a cyclic ether structure, a polymerizable monomer that is a raw material of a repeating unit represented by Formula (2) and a raw material of a repeating unit represented by Formula (3) The polymerizable monomer which becomes becomes.

A polymerizable monomer that is a raw material of a repeating unit containing a cyclic ether structure is a compound having an active hydrogen and a cyclic ether structure in the molecule, and a compound having a functional group that reacts with an unsaturated double bond and active hydrogen in the molecule. It can manufacture by making these react.
Examples of the compound having an active hydrogen and a cyclic ether structure in the molecule include glycidyl alcohol and 3-hydroxymethyl-3-ethyloxetane.
Examples of the compound having a functional group capable of reacting with an unsaturated double bond and active hydrogen in the molecule include acrylic acid chloride, methacrylic acid chloride, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, and vinyl benzoyl. Chloride.

  As a polymerizable monomer used as the raw material of the repeating unit represented by Formula (2), glycidyl acrylate, glycidyl methacrylate, 2-glycidyl ethyl acrylate, and 2-glycidyl ethyl methacrylate are mentioned, for example.

  As a polymerizable monomer used as the raw material of the repeating unit represented by Formula (3), 3-acryloyloxymethyl-3-ethyloxetane and 3-methacryloyloxymethyl-3-ethyloxetane are mentioned, for example.

  As a polymerizable monomer containing a 1st functional group, the monomer which has either the isocyanato group blocked with the blocking agent, the isothiocyanate group blocked with the blocking agent, and an unsaturated bond is mentioned, for example. A monomer having any of an isocyanato group blocked with the blocking agent and an isothiocyanato group blocked with the blocking agent and an unsaturated bond includes a compound having either an isocyanato group, an isothiocyanato group, and an unsaturated bond; It can be produced by reacting with an agent. As the unsaturated bond, a double bond is preferable.

Examples of the compound having a double bond and an isocyanato group include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl isocyanate.
Examples of the compound having a double bond and an isothiocyanato group include 2-acryloyloxyethyl isothiocyanate, 2-methacryloyloxyethyl isothiocyanate, and 2- (2′-methacryloyloxyethyl) oxyethyl isothiocyanate. .

  The said blocking agent can be used suitably for manufacture of the polymerizable monomer containing a 1st functional group. Isocyanato group or isothiocyanato group blocked with blocking agent by reacting isocyanato group or isothiocyanato group and unsaturated bond in the molecule with blocking agent In the reaction for producing a monomer having in the molecule, an organic solvent, a catalyst or the like can be added as necessary.

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

  Examples of the monomer having an isothiocyanato group blocked with a blocking agent and a double bond include 2- [O- [1′-methylpropylideneamino] thiocarboxyamino] ethyl-methacrylate and 2- [N -[1 ', 3'-dimethylpyrazolyl] thiocarbonylamino] ethyl-methacrylate.

The polymer compound (A-2) containing the repeating unit represented by the formula (1) and the repeating unit represented by the formula (6) is, for example, a raw material for the repeating unit represented by the formula (1). It can be produced by a method similar to the production of the polymer compound (A) using a polymerizable monomer mixture containing a polymerizable monomer and a polymerizable monomer that is a raw material of the repeating unit represented by formula (6). I can do it.
At least one repeating unit selected from the group consisting of a repeating unit represented by the formula (1), a repeating unit containing a cyclic ether structure and a repeating unit containing the following first functional group; The polymer compound (A-3) containing the repeating unit represented by formula (1), for example, is a polymerizable monomer that is a raw material of the repeating unit represented by formula (1), and the repeat represented by formula (2). Selected from the group consisting of a polymerizable monomer that is a raw material of the unit, a polymerizable monomer that is a raw material of the repeating unit represented by Formula (3), and a polymerizable monomer that is a raw material of the repeating unit containing the first functional group In the same manner as in the production of the polymer compound (A), a polymerizable monomer mixture containing at least one polymerizable monomer and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (6) is used. It can be produced by the method.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (6) include tert-butyl-4-vinylbenzoate, (2-methyl-2-adamantyl) -4-vinylbenzoate, and (tetrahydro -2-pyranyl] -4-vinylbenzoate, 4- (methoxymethoxy) styrene, 4- (methoxyethoxymethoxy) styrene, 4- (1-ethoxyethoxy) styrene, 4- (2-tetrahydropyranyloxy) styrene, 4- (cyclopropylmethoxy) styrene and 4- (cyclohexyloxy) styrene are mentioned.

  The polymer compound of the present invention contains a polymerizable monomer that is a raw material for the repeating unit represented by the formula (1), a polymerizable monomer that is a raw material for the repeating unit containing a cyclic ether structure, and a first functional group. A polymerizable monomer other than the polymerizable monomer serving as the raw material for the repeating unit and the polymerizable monomer serving as the raw material for the repeating unit represented by the formula (6) may be added during the polymerization.

  Additional polymerizable monomers used include, for example, acrylic acid esters and derivatives thereof, methacrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof. Organic carboxylic acid vinyl esters and derivatives thereof, organic carboxylic acid allyl esters and derivatives thereof, fumaric acid dialkyl esters and derivatives thereof, maleic acid dialkyl esters and derivatives thereof, itaconic acid dialkyl esters and derivatives thereof, organic carboxylic acids N-vinylamide derivatives of acids, terminal unsaturated hydrocarbons and derivatives thereof, organogermanium derivatives containing unsaturated hydrocarbon groups, vinyl-1,3-dioxolan-2-one and derivatives thereof, acrylamide and derivatives thereof Body, and the like.

  The kind of the polymerizable monomer that is additionally used is appropriately selected according to the use of the polymer compound of the present invention such as characteristics required for the insulating layer. From the viewpoint of excellent durability against solvents and reducing the hysteresis of organic thin film transistors, monomers that have high molecular density and form a hard film are selected in films containing these compounds, such as styrene and styrene derivatives. . Further, from the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode or the surface of the substrate, the polymer compound of the present invention is made plastic such as methacrylic acid ester and derivatives thereof, acrylic acid ester and derivatives thereof. The monomer to be imparted is selected.

  The acrylate ester and its derivative may be a monofunctional acrylate or a polyfunctional acrylate although the amount of use is limited. Examples of acrylic acid esters and derivatives thereof include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-sec-butyl, and acrylic acid. Hexyl, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic Acid-3-hydroxypropyl, 2-hydroxybutyl acrylate, 2-hydroxyphenylethyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol di Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N-acryloylmorpholine Is mentioned.

  The methacrylic acid ester and derivatives thereof may be monofunctional methacrylates, and may be polyfunctional methacrylates although the amount of use is limited. Examples of methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, methacryl Acid-sec-butyl, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, meta 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, ethylene glycol Coal dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol penta Examples include methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-acryloylmorpholine.

  Examples of styrene and derivatives thereof include styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and 2,5-dimethylstyrene. 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m -Ethylstyrene, p-ethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p -Methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydride Xylstyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyl Toluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl -Α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene and 4-aminostyrene.

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

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

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

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

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

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

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

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

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

  Examples of acrylamide and derivatives thereof include N, N-dimethylacrylamide, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, and N- (3- (N ′, N′-dimethylaminopropyl) acrylamide. It is done.

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

  In the production of the polymer compound of the present invention, the charged molar amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (1) is preferably 10 mol% or more and 95% among all polymerizable monomers involved in the polymerization. The mol% or less, more preferably 20 mol% or more and 90 mol% or less. If the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is less than 10 mol%, the liquid repellency becomes insufficient and pattern formation may not be possible. When the molar amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (1) exceeds 95 mol%, the crosslinking rate may be lowered, and the solvent resistance may be deteriorated.

  When the polymer compound of the present invention contains a repeating unit containing a cyclic ether structure, the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit containing a cyclic ether structure in the production of the polymer compound is involved in the polymerization. Among all the polymerizable monomers to be used, the amount is preferably 5 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 40 mol% or less. If the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit containing a cyclic ether structure is less than 5 mol%, the formation of a crosslinked structure may be insufficient and the solvent resistance may be lowered. If the charged molar amount of the polymerizable monomer serving as the raw material for the repeating unit containing a cyclic ether structure exceeds 40 mol%, the liquid repellency may be insufficient and pattern formation may not be possible.

  When the polymer compound of the present invention includes a repeating unit containing the first functional group, the charged molar amount of the polymerizable monomer containing the first functional group in the production of the polymer compound is all involved in the polymerization. In the polymerizable monomer, it is preferably 5 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 40 mol% or less. By adjusting the charged molar amount of the polymerizable monomer containing the first functional group within this range, a sufficient crosslinked structure is formed inside the insulating layer, and the solvent resistance is enhanced.

  In the production of the polymer compound (A-2) or the polymer compound (A-3), the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (6) is the amount of all polymerizations involved in the polymerization. In the functional monomer, it is preferably 5 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 40 mol% or less. If the charged molar amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (6) is less than 5 mol%, the formation of a crosslinked structure may be insufficient and the solvent resistance may be lowered. When the charged molar amount of the polymerizable monomer serving as the raw material of the repeating unit represented by formula (6) exceeds 50 mol%, the liquid repellency becomes insufficient and pattern formation may not be possible.

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

  Examples of the polymer compound (A) include poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl. Methacrylate-co-2-hydroxyethyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl Methacrylate-co-2-isocyanatoethyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) Benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5- Toxi-2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-) Nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl Methacrylate-co-2- (methacryloyloxyethyl) methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-) Nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-N, N, -diethylacrylamide), poly (α- Til- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-N, N, -diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- 2- (methacryloyloxyethyl) methacrylate-co-N, N, -diethylacrylamide), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy- 2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-N, N, -diethylacrylamide), poly (α-methyl- (4 (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-N, N, -diethylacrylamide), and Poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co- N, N, -diethylacrylamide).

  Examples of the polymer compound (A-1) include poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro. ) Benzyl methacrylate-co-glycidyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate -Co- (3-ethyl-3-oxetanyl) methyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy- 2-Nitro) benzyl methacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (α-methyl- (4- (3,3,4) , 4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl- Methacrylate]), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate- Co-methyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- ( 3-ethyl-3-oxetanyl) methyl methacrylate-co-methyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-he) Tafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-methyl methacrylate), poly ( α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 ′-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-methyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl)) Oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-N, N-diethylacrylamide), poly (α Methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate -Co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl Methacrylate-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3 , 4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyra] Ryl) carbonylamino] ethyl-methacrylate] -co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy- 5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy -5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile), poly (α-methyl- (4- (3,3,4,4,5) , 5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropiyl) Denamino) carboxyamino] ethyl-methacrylate] -co-acrylonitrile), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2 -Nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-acrylonitrile), poly (α-methyl- (4- (3 3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile-co-N, N-diethylacrylamide), poly ( α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro ) Benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,4)) 5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- Acrylonitrile-co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) Benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -core Rilonitrile-co-N, N-diethylacrylamide), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) Benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile-co-methyl methacrylate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5- Methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-methyl methacrylate), poly (α-methyl- (4- (3,3,4,4) , 5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1 -Methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-acrylonitrile-co-methyl methacrylate) and poly (α-methyl- (4- (3,3,4,4,5,5,5- Heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-acrylonitrile-co- Methyl methacrylate).

  Examples of the polymer compound (A-2) include poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro. ) Benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-hepta) Fluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3 3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co- -(1-ethoxyethoxy) styrene), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2 -Hydroxyethyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-) Nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) ) Oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co-4- (1-ethoxyethoxy) styrene ), Poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-hydroxyethyl Methacrylate-co-N, N, -diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-hepta) Fluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-N, N, -diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly ( α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methac Liloyloxyethyl) methacrylate-co-N, N, -diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (2,3,4,5,6-) Pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-N, N, -diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly ( α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-N, N, -Diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (2,3,4,5,6-pentafluoro) Benzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co-N, N, -diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (Α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-) Nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoe G), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyl) Oxyethyl) methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy -2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (2,3,4,5, 6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co- (2-the Lahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (Methacryloyloxyethyl) methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) ) Oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-N, N, -diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly ( α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-ni Toro) benzyl methacrylate-co-2-isocyanatoethyl methacrylate-co-N, N, -diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- ( 3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co-N, N, -diethyl Acrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-) Nitro) benzyl methacrylate-co-2-hydroxyethyl methacrylate-co-N, N, -diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (2,3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate -Co-2-isocyanatoethyl methacrylate-co-N, N, -diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate) and poly (α-methyl- (4- (2, 3,4,5,6-pentafluorobenzyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-2- (methacryloyloxyethyl) methacrylate-co-N, N, -diethylacrylamide-co- (2 -Tetrahydropyranyl) -4-vinylbenzoate).

Examples of the polymer compound (A-3) include poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro. ) Benzyl methacrylate-co-glycidyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl)) Oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- ( 3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) cal Xylamino] ethyl-methacrylate] -co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy- 5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-4- (1-ethoxyethoxy) styrene) , Poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-methyl Methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-meth) Xyl-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxy Amino] ethyl-methacrylate] -co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-hepta Fluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl- Tacrylate] -co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy) -5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3 , 3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-N, N- Diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropenthi) ) Oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-N, N-diethylacrylamide-co- 4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl Methacrylate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene) , Poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- Glycidyl methacrylate-co-acrylonitrile-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-) 5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4 -(3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) Carboxyamino] ethyl-methacrylate] -co-acrylonitrile-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4) 4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate ] -Co-acrylonitrile-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5 -Methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile-co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl 3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4) , 5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co -Acrylonitrile-co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5-hepta) Fluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl Ru-methacrylate] -co-acrylonitrile-co-N, N-diethylacrylamide-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5) , 5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile-co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (Α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl ) Methyl methacrylate-co-acrylonitrile-co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-me Ru- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methyl Propylideneamino) carboxyamino] ethyl-methacrylate] -co-acrylonitrile-co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4, 4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate ] -Co-acrylonitrile-co-methyl methacrylate-co-4- (1-ethoxyethoxy) styrene), poly (α-methyl- (4- (3,3,4,4,5,5,5) Heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3 3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co- (2-tetrahydropyrani ) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate- Co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- (2-teto Hydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate- Co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- ( 4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-methyl methacrylate-co- (2-tetrahydro Pyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-) 5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-methyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α- Methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methyl Propylideneamino) carboxyamino] ethyl-methacrylate] -co-methylmethacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4) , 5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5 ' Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-methyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,4)) 5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-N, N-diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinyl Benzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl -3-Oxetanyl) methyl methacrylate-co-N, N-diethylacrylamide-co- (2-tetrahydropyra Nyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate- Co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-N, N-diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), Poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1′- (3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-N, N-diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylben Acid), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co -Acrylonitrile-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly ([alpha] -methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5 -Methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate -Co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-acrylonitrile-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α- Methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-acrylonitrile-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4) 4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile -Co-N, N-diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5- Heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-N, N-diethylacrylamide-co- (2-tetrahydro Pyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate -Co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-acrylonitrile-co-N, -Diethylacrylamide-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy- 5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-acrylonitrile-co-N, N-diethylacrylamide -Co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy) -2-Nitro) benzyl methacrylate-co-glycidyl methacrylate-co-acrylonitrile-co-methyl methacrylate-co- (2-tetrahydro Ranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate- Co- (3-ethyl-3-oxetanyl) methyl methacrylate-co-acrylonitrile-co-methyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate), poly (α-methyl- (4- (3 , 3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] Ethyl-methacrylate] -co-acrylonitrile-co-methyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate ) And poly (α-methyl- (4- (3,3,4,4,5,5,5-heptafluoropentyl) oxy-5-methoxy-2-nitro) benzyl methacrylate-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-acrylonitrile-co-methyl methacrylate-co- (2-tetrahydropyranyl) -4-vinylbenzoate).

<Insulating layer material>
The insulating layer material of this invention contains the high molecular compound containing the repeating unit represented by Formula (1). Further, it may contain a solvent, an additive and the like for mixing and viscosity adjustment. Examples of the solvent include ether solvents such as tetrahydrofuran and dibutyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic carbonization such as xylene. Examples thereof include a hydrogen solvent, a ketone solvent such as acetone, an acetate solvent such as butyl acetate, an alcohol solvent such as isopropyl alcohol, a halogen solvent such as chloroform, and a mixed solvent of these solvents. As the solvent, an organic solvent having a boiling point of 100 ° C. to 200 ° C. at normal pressure is preferable. Examples of organic solvents having a boiling point of 100 ° C. to 200 ° C. at normal pressure include 2-heptanone (boiling point 151 ° C.) and propylene glycol monomethyl ether acetate (boiling point 146 ° C.). Moreover, as an additive, a sensitizer, a leveling agent, a viscosity modifier, and a hardening accelerator are mentioned, for example.

One aspect of the method for forming an insulating layer of the present invention is:
Applying a liquid containing an insulating layer material to a substrate to form a coating layer on the substrate;
Applying heat to the coating layer;
Forming a lyophilic and liquid-repellent pattern by irradiating a part of the coating layer to which heat is applied through a mask with an electromagnetic wave or an electron beam;
Is a method of forming an insulating layer including
Here, the “base material” refers to a component member on which an insulating layer is disposed.

  The electromagnetic waves are preferably ultraviolet rays.

  The coating layer is formed, for example, by preparing a liquid containing an insulating layer material (insulating layer coating liquid) and applying the insulating layer coating liquid to the substrate. Examples of the coating method include a spin coating method, a die coater method, a screen printing method, and an ink jet method. The formed coating layer is dried as necessary. Drying here means removing the solvent contained in the applied insulating layer material.

Next, the coating layer is cured by applying heat. When the polymer compound of the present invention contains a repeating unit containing a cyclic ether structure, and the insulating layer material contains a compound that generates an acid by heating, the cyclic ether moiety reacts with the acid generated by heating, and the polymer The compound is cationically polymerized to form a crosslinked structure, and an insulating layer is formed.
When the polymer compound of the present invention includes a repeating unit containing the first functional group, the second functional group is formed by heating, and the site of the second functional group reacts with moisture in the atmosphere. The compound forms a crosslinked structure, and an insulating layer is formed. further,
When the polymer compound of the present invention contains a repeating unit containing a cyclic ether structure and a repeating unit containing a first functional group, and the insulating layer material contains a compound that generates an acid by heating, the acid generated by heating The cyclic ether site reacts, and the hydroxyl group generated by cationic polymerization of the polymer compound reacts with the second functional group generated from the first functional group to form a crosslinked structure, thereby forming an insulating layer. Is done.

（Ｙ） Next, the formed insulating layer is selectively irradiated with an electromagnetic wave or an electron beam through a mask. By irradiation with an electromagnetic wave or electron beam, the site of the formula (Y) in the repeating unit represented by the formula (1) was detached from the polymer compound of the present invention to generate an acid, and the electromagnetic wave or the electron beam was irradiated. The part is hydrophilized. The portion of the insulating layer irradiated with electromagnetic waves or electron beams has lyophilic properties, the portion of the insulating layer shielded with electromagnetic waves or electron beams by a mask has lyophobic properties, and lyophilic patterns depending on the mask shape and A liquid repellent pattern is formed.

(Y)

  When irradiating an electromagnetic wave, the wavelength of the electromagnetic wave is preferably 450 nm or less, more preferably 150 to 410 nm. When the wavelength of the electromagnetic wave to be irradiated exceeds 450 nm, the site of the formula (Y) is not sufficiently detached, the hydrophilicity is insufficient, and pattern formation may not be possible. As electromagnetic waves, ultraviolet rays are preferable.

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

  The insulating layer is preferably washed with an organic solvent after being selectively irradiated with electromagnetic waves or electron beams through a mask. The organic solvent is not particularly limited as long as it does not dissolve the insulating layer, but preferably has a boiling point of 50 ° C to 200 ° C. Examples of the organic solvent include ethanol, isopropanol, toluene, 2-heptanone, and propylene glycol monomethyl ether acetate. After washing, heating and drying may be performed. Heating can be performed using a heater, an oven, or the like.

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

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

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

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

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

One aspect of a method for forming an organic thin film transistor insulating layer using the insulating layer material of the present invention is as follows:
Applying a liquid containing an insulating layer material to a substrate to form a coating layer on the substrate;
Applying heat to the coating layer;
Forming a lyophilic and liquid-repellent pattern by irradiating a part of the coating layer to which heat is applied through a mask with an electromagnetic wave or an electron beam;
Forming a wiring layer and an organic semiconductor layer by an ink jet method or a printing method on the insulating layer on which the lyophilic and liquid repellent patterns are formed;
Is a method for forming an organic thin film transistor insulating layer.

  The insulating layer is preferably a gate insulating layer. The gate insulating layer is formed by, for example, preparing a liquid containing an insulating layer material (insulating layer coating liquid), applying the insulating layer coating liquid to the substrate, drying, baking, and selectively This is done by irradiating with an electron beam and making the irradiated part hydrophilic.

  The method for applying the insulating layer coating solution is the same as the method described in the method for forming the insulating layer.

  The organic semiconductor layer is formed by applying an ink made of an organic transistor organic semiconductor material onto the insulating layer to which the mask pattern has been transferred by an inkjet method or a printing method. An organic thin film transistor can be manufactured by forming an organic semiconductor layer.

  A wiring layer may be formed on the insulating layer. The wiring layer is formed by applying an ink made of a wiring material onto the insulating layer to which the mask pattern is transferred by an ink jet method or a printing method.

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

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

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

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

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

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

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

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

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

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

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

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

Synthesis example 1
(Synthesis of Compound 1)
A Dimroth with a three-way cock attached to the top was attached to a 500 ml three-necked flask, and 17 ′ g of 3′-hydroxy-4′-methoxyacetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) , 3,4,5,6-pentafluorobenzyl bromide (Aldrich) 205.00g, potassium carbonate (Wako Pure Chemical Industries) 20.42g, N, N-dimethylformamide (Wako Pure Chemical Industries) 200 ml and a stirrer were added, and the mixture was reacted at room temperature for 24 hours while stirring the stirrer with a magnetic stirrer. After completion of the reaction, the reaction mixture was placed in a 1 L beaker containing 500 ml of ion exchange water. The precipitate was filtered off and further washed thoroughly with ion exchange water, and then dried under reduced pressure to obtain Compound 1 as a white solid. The yield of Compound 1 was 31.83 g, and the yield was 96%.

化合物１ ¹ H NMR (acetone-d6, δ ppm TMS standard): 7.67-7.64 (d, 1H), 7.57 (s, 1H), 7.25-7.22 (d, 1H), 5. 35 (s, 2H), 3.88 (s, 3H), 2.55 (s, 3H)
The measurement was performed using a 300 MHz NMR apparatus (INOVA; manufactured by VARIAN).

Compound 1

Synthesis example 2
(Synthesis of Compound 2)
A Dimroth with a three-way cock attached to the top is attached to a 1000 ml three-necked flask. In the three-necked flask, 31.83 g of compound 1, 400 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and a stirrer Then, a homogeneous solution was prepared while stirring the stirring bar with a magnetic stirrer. To the obtained solution, 3.61 g of sodium borohydride (Wako Pure Chemical Industries, Ltd.) was added in 5 portions. After completion of the addition, the reaction was allowed to proceed for 24 hours at room temperature. After completion of the reaction, the reaction solution was concentrated with a rotary evaporator until the volume became about 1/10, 200 ml of diethyl ether was added and dissolved again, and then transferred to a 500 ml separatory funnel. The diethyl ether layer was washed with 50 ml of ion exchange water three times and then dried over anhydrous magnesium sulfate. The insoluble material was filtered off, concentrated with a rotary evaporator, and the solvent was removed with a vacuum desiccator to obtain Compound 2 as a transparent and viscous liquid. The yield of Compound 2 was 31.69 g, and the yield was 99%.

化合物２ ¹ H NMR (acetone-d6, δ ppm): 7.07 (s, 1H), 7.00-6.97 (d, 1H), 6.89-6.86 (d, 1H), 5.21- 5.16 (d, 2H), 4.82-4.76 (q, 1H), 3.81 (s, 3H), 1.43-1.37 (d, 3H).
The measurement was performed using a 300 MHz NMR apparatus (INOVA; manufactured by VARIAN).

Compound 2

Synthesis example 3
(Synthesis of Compound 3)
Into a 200 ml eggplant flask, 24.7 g of compound 2, 60 ml of acetonitrile, and a stirrer were placed, and the stirrer was stirred with a magnetic stirrer to prepare a uniform solution. While the eggplant flask was immersed in an ice bath and cooled, 60 ml of concentrated nitric acid (d = 1.42 g / cm ³ ) cooled in the ice bath was slowly dropped into the eggplant flask. After completion of dropping, the mixture was further stirred for 1 hour in an ice bath to be reacted. After completion of the reaction, the reaction mixture was placed on 400 ml of crushed ice in a 500 ml disposable cup and neutralized with an aqueous sodium hydroxide solution. After neutralization, the aqueous layer was transferred to a 1 L separatory funnel, and a solution prepared by dissolving the precipitate remaining in the disposable cup in 100 ml of ethyl acetate was transferred to a 1 L separatory funnel to separate the organic layer. The aqueous layer was further extracted three times with 50 ml of ethyl acetate, all the organic layers were combined, washed with 200 ml of ion-exchanged water, and liquid separation was repeated three times. The organic layer was separated and dried over magnesium sulfate, the insoluble material was filtered off, and the filtrate was concentrated on a rotary evaporator to obtain a yellow viscous liquid. 200 ml of diethyl ether was added to the obtained yellow viscous liquid, and the precipitate was separated by filtration. The precipitate was further washed three times with 50 ml of diethyl ether, and all the filtrates were combined and concentrated with a rotary evaporator to obtain a pale yellow viscous liquid. The obtained pale yellow viscous liquid was purified with a silica gel column using a mixed solvent in which ethyl acetate and hexane were mixed at a volume ratio of 3: 7 as a developing solvent, and the second fraction was fractionated to obtain Compound 3. Obtained. The yield of compound 3 was 12.00 g, and the yield was 43%.

化合物３ ¹ H NMR (acetone-d6, δ ppm): 7.77 (s, 1H), 7.53 (s, 1H), 5.50-5.46 (m, 1H), 5.38 (s, 2H) 3.97 (s, 3H), 2.86 (br, 1H) 1.47-1.45 (d, 3H).
The measurement was performed using a 300 MHz NMR apparatus (INOVA; manufactured by VARIAN).

Compound 3

Example 1
(Synthesis of Compound 4)
A Jimroth with a three-way cock attached to the top was attached to a 200 ml three-necked flask. In the three-necked flask, 12.00 g of compound 3, 6.78 g of triethylamine (Wako Pure Chemical Industries, Ltd.), dehydrated tetrahydrofuran 100 ml (made by Wako Pure Chemical Industries, Ltd.) and a stirrer were added, the air inside the flask was replaced with nitrogen, and the stirrer was stirred with a magnetic stirrer to prepare a uniform solution. To the obtained solution, 6.38 g of methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped with a gas tight syringe. After completion of the dropwise addition, the reaction was allowed to proceed at room temperature for 18 hours, and then 40 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by further reaction at room temperature for 3 hours. After completion of the reaction, the reaction solution was transferred to a 1000 ml separatory funnel, 200 ml of diethyl ether was added, and the organic layer was washed with 400 ml of ion-exchanged water. After separating the aqueous layer, the organic layer was washed with dilute hydrochloric acid until the aqueous layer became acidic, and then washed with ion-exchanged water until the aqueous layer became neutral. The organic layer was dried over anhydrous magnesium sulfate, the insoluble matter was filtered off, the filtrate was concentrated with a rotary evaporator, and the solvent was removed with a rotary pump to obtain Compound 4 as a pale yellow viscous liquid. The yield of compound 4 was 10.24 g, and the yield was 73%.

化合物４ ¹ H NMR (acetone-d6, δ ppm): 7.83 (d, 1H), 7.31 (s, 1H), 6.45-6.40 (q, 1H), 6.19 (s, 1H) 5.68 (s, 1H), 5.41 (s, 2H), 3.97 (s, 3H), 1.93 (s, 3H), 1.69-1.65 (d, 3H).
The measurement was performed using a 300 MHz NMR apparatus (INOVA; manufactured by VARIAN).

Compound 4

化合物５ Synthesis example 4
(Synthesis of Compound 5)
In a 300 ml three-necked flask equipped with a three-way cock and septum, 33.29 g of 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., trade name: OXT-101), triethylamine (Wako Pure Chemical Industries, Ltd.) 48.31 g (manufactured by company), 200 ml of dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and a stirrer were placed, and the air inside the flask was replaced with nitrogen. The flask was immersed in an ice bath, and 25.00 g of methacryloyl chloride was slowly added dropwise using a gas tight syringe while stirring the reaction mixture by stirring the stirring bar with a magnetic stirrer. After completion of the dropwise addition, the mixture was further stirred in an ice bath for 2 hours, and then stirred overnight at room temperature for reaction. After completion of the reaction, the produced triethylamine hydrochloride was filtered off, the filtrate was transferred to a 500 ml separatory funnel, 200 ml of diethyl ether was added to the filtrate, the organic layer was washed with 100 ml of ion-exchanged water, and the organic layer was separated. Liquid. After washing the organic layer with water three times, the organic layer was separated and dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was filtered off, the filtrate was concentrated using a rotary evaporator to obtain Compound 5 as a light brown liquid. The yield of Compound 5 was 29.3 g, and the yield was 61.3%.

Compound 5

Example 2
(Synthesis of polymer compound 1)
In a 50 ml pressure vessel (ACE GLASS), 1.60 g of compound 4, 0.28 g of acrylonitrile (manufactured by Wako Pure Chemical Industries), 0.64 g of compound 5, methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.52 g, 2,2′-azobis (2-methylpropionitrile) 0.02 g, and propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) 4.58 g are added to purge dissolved oxygen. After bubbling with argon gas, it was sealed. Polymerization was carried out in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 1 was dissolved. The high molecular compound 1 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

高分子化合物１

Polymer compound 1

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 1 was 59000 (GPC made from Shimadzu, 1 Tskel super HM-H + 1 Tskel super H2000, mobile phase = THF).

Example 3
(Insulation layer formation and contact angle measurement)
In a 20 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of polymer compound 1 obtained in Example 2 and 0.012 g of TA-100 (manufactured by San Apro Co., Ltd.) which is a photoacid generator, propylene glycol 1.00 g of monomethyl ether acetate was added and dissolved while stirring to prepare a uniform coating solution 1 as an insulating layer material.

The obtained coating solution 1 was filtered using a membrane filter having a pore diameter of 0.45 μm, spin-coated on a silicon substrate, and then dried on a hot plate at 100 ° C. for 1 minute to form a coating layer. Thereafter, the coating layer was further baked at 120 ° C. for 5 minutes, and then the coating layer was irradiated with 800 mJ / cm ² of UV light (wavelength 365 nm) using an aligner (manufactured by Canon Inc .; PLA-521). Soaked for 2 minutes. The silicon substrate after immersion was washed with ion-exchanged water, dried with a spin dryer, and then dried at 100 ° C. for 1 minute in the air on a hot plate to form an insulating layer.

  About the produced insulating layer, the contact angle was measured using the contact angle measuring apparatus (CA-A; Kyowa Interface Science Co., Ltd. product). The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 4
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 3 except that the coating layer was irradiated with UV light (wavelength 365 nm) of 1600 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 5
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 3 except that the coating layer was irradiated with UV light (wavelength 365 nm) of 2400 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 6
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 3 except that the coating layer was not irradiated with UV light (wavelength 365 nm) by an aligner (manufactured by Canon Inc .; PLA-521), and the contact angle of ion-exchanged water was measured. did. The results are shown in Table 1. Since the irradiation with UV light was not performed, the insulating layer had liquid repellency.

高分子化合物２ Example 7
(Synthesis of polymer compound 2)
In a 50 ml pressure vessel (manufactured by ACE GLASS), 1.60 g of compound 4, 0.09 g of acrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.), 0.32 g of compound 5, N, N-diethylacrylamide (Ki Inoue Co., Ltd.) 0.22 g, 0.01 g of 2,2′-azobis (2-methylpropionitrile), and 3.36 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to purge dissolved oxygen. Therefore, after bubbling with argon gas, it was sealed. Polymerization was carried out in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 2 was dissolved. The high molecular compound 2 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

Polymer compound 2

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 2 was 30000 (Shimadzu GPC, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Example 8
(Insulation layer formation and contact angle measurement)
In a 20 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of polymer compound 2 obtained in Example 7 and 0.012 g of TA-100 (manufactured by San Apro Co., Ltd.) which is a photoacid generator, propylene glycol 1.00 g of monomethyl ether acetate was added and dissolved while stirring to prepare a uniform coating solution 2 as an insulating layer material.

  An insulating layer was formed in the same manner as in Example 3 except that the coating solution 2 was used instead of the coating solution 1, and the contact angle of ion-exchanged water was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 9
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 8 except that the coating layer was irradiated with 1600 mJ / cm ² of UV light (wavelength 365 nm) using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 10
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 8 except that the coating layer was irradiated with UV light (wavelength 365 nm) of 2400 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 11
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 8 except that the coating layer was not irradiated with UV light (wavelength 365 nm) using an aligner (manufactured by Canon Inc .; PLA-521), and the contact angle of ion-exchanged water was measured. did. The results are shown in Table 1. Since the irradiation with UV light was not performed, the insulating layer had liquid repellency.

高分子化合物３ Example 12
(Synthesis of polymer compound 3)
In a 50 ml pressure vessel (manufactured by ACE GLASS), 2.72 g of compound 4, 0.54 g of compound 5, 0.02 g of 2,2′-azobis (2-methylpropionitrile), propylene glycol monomethyl ether acetate ( 4.95 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, bubbled with argon gas to purge dissolved oxygen, and then sealed. Polymerization was carried out in an oil bath at 80 ° C. for 8 hours to obtain a viscous propylene glycol monomethyl ether acetate solution in which the polymer compound 3 was dissolved. The high molecular compound 3 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

Polymer compound 3

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 23 was 31000 (GPC made from Shimadzu, one Tskel super HM-H + one Tskel super H2000, a mobile phase = THF).

Example 13
(Insulation layer formation and contact angle measurement)
In a 20 ml sample bottle, 1.00 g of the propylene glycol monomethyl ether acetate solution of the polymer compound 3 obtained in Example 12 and 0.012 g of TA-100 (manufactured by San Apro Co., Ltd.) which is a photoacid generator, propylene glycol 1.00 g of monomethyl ether acetate was added and dissolved while stirring to prepare a uniform coating solution 3 as an insulating layer material.

  An insulating layer was formed in the same manner as in Example 3 except that the coating solution 3 was used in place of the coating solution 1, and the contact angle of ion-exchanged water was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 14
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 13 except that the coating layer was irradiated with UV light (wavelength 365 nm) of 1600 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

(Insulation layer formation and contact angle measurement)
Example 15
An insulating layer was formed in the same manner as in Example 13 except that the coating layer was irradiated with UV light (wavelength 365 nm) of 2400 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 16
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 13 except that the coating layer was not irradiated with UV light (wavelength 365 nm) by an aligner (manufactured by Canon Inc .; PLA-521), and the contact angle of ion-exchanged water was measured. did. The results are shown in Table 1. Since the irradiation with UV light was not performed, the insulating layer had liquid repellency.

Example 17
(Insulation layer formation and contact angle measurement)
In a 20 ml sample bottle, 0.25 g of the propylene glycol monomethyl ether acetate solution of polymer compound 3 obtained in Example 12, 0.50 g of cresol novolac type epoxy resin (YDCN-704, manufactured by Toto Kasei Co., Ltd.), light 0.018 g of TA-100 (manufactured by San Apro Co., Ltd.) and 2.80 g of propylene glycol monomethyl ether acetate were added and dissolved while stirring to prepare a uniform coating solution 4 as an insulating layer material.

  An insulating layer was formed in the same manner as in Example 3 except that the coating solution 4 was used instead of the coating solution 1, and the contact angle of ion-exchanged water was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 18
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 17 except that the coating layer was irradiated with 1600 mJ / cm ² of UV light (wavelength 365 nm) using an aligner (PLA-521, manufactured by Canon Inc.), and ion-exchanged water. The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 19
(Insulation layer formation and contact angle measurement)
An insulating layer is formed in the same manner as in Example 17 except that the coating layer is irradiated with UV light (wavelength 365 nm) of 2400 mJ / cm ² using an aligner (manufactured by Canon Inc .; PLA-521). The contact angle of was measured. The results are shown in Table 1. The insulating layer irradiated with UV light was lyophilic.

Example 20
(Insulation layer formation and contact angle measurement)
An insulating layer was formed in the same manner as in Example 17 except that the coating layer was not irradiated with UV light (wavelength 365 nm) using an aligner (manufactured by Canon Inc .; PLA-521), and the contact angle of ion-exchanged water was measured. did. The results are shown in Table 1. Since the irradiation with UV light was not performed, the insulating layer had liquid repellency.

  From Examples 3-6, Examples 8-11, and Examples 13-20, the same lyophilic pattern as the mask shape can be formed on the insulating layer by irradiating the insulating layer with UV light through the mask. Recognize.

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

Claims (14)

The high molecular compound containing the repeating unit represented by Formula (1).

(1)
[Wherein, R ¹ represents a hydrogen atom or a methyl group. R and R ² each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^f represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. A ¹ represents a divalent group. n represents an integer of 1 to 4. When there are a plurality of R, they may be the same or different. When there are a plurality of ^Rf , they may be the same or different. a represents an integer of 0 or 1. ] The polymer compound according to claim 1, further comprising at least one repeating unit selected from the group consisting of a repeating unit containing a cyclic ether structure and a repeating unit containing the following first functional group.

First functional group: a functional group capable of generating a second functional group capable of reacting with active hydrogen by the irradiation of electromagnetic waves or the action of heat. The polymer compound according to claim 2, wherein the repeating unit containing a cyclic ether structure is a repeating unit represented by the formula (2) or a repeating unit represented by the formula (3).

(2)
[Wherein R ³ represents a hydrogen atom or a methyl group. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^a represents a divalent group. t represents an integer of 0 or 1. ]

(3)
[Wherein, R ⁷ represents a hydrogen atom or a methyl group. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^d represents a divalent group. w represents an integer of 0 or 1. ]   The polymer compound according to claim 2, wherein the first functional group is an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent. The polymer compound according to claim 4, wherein the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are groups represented by the formula (4).

(4)
[Wherein, X ^a represents an oxygen atom or a sulfur atom, and R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ] The polymer compound according to claim 4, wherein the isocyanato group blocked with the blocking agent and the isothiocyanato group blocked with the blocking agent are groups represented by the formula (5).

(5)
[Wherein, X ^b represents an oxygen atom or a sulfur atom, and R ¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ] Furthermore, the high molecular compound as described in any one of Claims 1-6 containing the repeating unit represented by Formula (6).

(6)
[Wherein, R ¹³ represents a hydrogen atom or a methyl group. R ^b represents a divalent group. R ¹⁴ represents an organic group that can be eliminated by an acid. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A ² represents —O— or —COO—. u represents an integer of 0 or 1, and m represents an integer of 1 to 5. When there are a plurality of A ² —R ¹⁴ , they may be the same or different. When there are a plurality of R ′, they may be the same or different. ] The compound represented by Formula (7).

(7)
[Wherein, R ¹ and R each represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. R ^f represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. A ¹ represents a divalent group. R ² represents a hydrogen atom or a methyl group. a represents 0 or 1; When there are a plurality of R, they may be the same or different. When there are a plurality of ^Rf , they may be the same or different. n represents an integer of 1 to 4. ]   The insulating layer material containing the high molecular compound as described in any one of Claims 1-7. Applying the liquid containing the insulating layer material according to claim 9 to a base material to form a coating layer on the base material;
Applying heat to the coating layer and curing; and irradiating a part of the cured coating layer through a mask with an electromagnetic wave or an electron beam to form a lyophilic and liquid-repellent pattern;
Forming an insulating layer including   The method for forming an insulating layer according to claim 10, wherein the electromagnetic waves are ultraviolet rays.   The organic thin-film transistor which has an insulating layer formed using the insulating-layer material of Claim 9.   The member for a display containing the organic thin-film transistor of Claim 12.   A display comprising the display member according to claim 13.

Images