JP5890633B2 - Composition for organic thin film transistor insulating layer and organic thin film transistor - Google Patents

Description

  The present invention relates to an organic thin film transistor insulating layer composition suitable for forming an insulating layer of an organic thin film transistor, and particularly to an organic thin film transistor insulating layer composition suitable for forming an overcoat insulating layer.

  Since an organic thin film transistor can be manufactured at a lower temperature than an inorganic semiconductor, a plastic substrate or a film can be used as the substrate. By using such a substrate, an element that is flexible, lightweight, and hardly broken can be obtained. In some cases, an element can be manufactured by application of a solution containing an organic material or film formation using a printing method, and a large number of elements can be manufactured on a large-area substrate at low cost.

  In addition, since there are a wide variety of materials that can be used for studying transistors, if materials having different molecular structures are used for studying, elements having a wide range of characteristics can be manufactured.

  In a field effect organic thin film transistor which is a kind of organic thin film transistor, a voltage applied to a gate electrode acts on a semiconductor layer through a gate insulating layer to control the amount of drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer.

  An organic semiconductor compound used for a field effect organic thin film transistor is easily affected by an environment such as humidity and oxygen, and the transistor characteristics are likely to deteriorate with time due to humidity, oxygen and the like.

  Therefore, in the bottom gate type organic field effect transistor element structure in which the organic semiconductor compound is exposed, it is essential to form an overcoat layer covering the entire element structure to protect the organic semiconductor compound from contact with the outside air. . On the other hand, in the top gate type organic field effect transistor element structure, the organic semiconductor compound is coated and protected by a gate insulating layer.

  Thus, in order to form the overcoat insulating layer or gate insulating layer which covers the organic-semiconductor layer in a field effect type organic thin-film transistor, the composition containing a high molecular compound and a solvent is used. In the present specification, an insulating layer or an insulating film of an organic thin film transistor such as the overcoat insulating layer and the gate insulating layer is referred to as an organic thin film transistor insulating layer.

  As a material constituting the organic thin film transistor insulating layer (hereinafter referred to as an organic thin film transistor insulating layer material), for example, a copolymer containing tetrafluoroethylene has been proposed (Patent Document 1).

JP-T-2005-513788

  However, when oxygen or moisture in the atmosphere enters the organic thin film transistor, it acts on the organic semiconductor compound, a charge trap is formed, and the absolute value of the threshold voltage increases. Therefore, an organic field effect transistor including an insulating layer formed using the organic thin film transistor insulating layer material has a problem that the absolute value of the threshold voltage when driven in the atmosphere is large.

  The objective of this invention is providing the composition for organic thin-film transistor insulating layers which can manufacture the organic thin-film transistor with a small absolute value of the threshold voltage when driving in air | atmosphere.

  That is, this invention provides the composition for organic thin-film transistor insulating layers containing the compound (A) containing group which has a cyclic ether structure, and a fluorine-containing solvent (B).

  In one certain form, group which has the said cyclic ether structure is Formula (1).

（１）

(1)

[In formula, R < ₁ > -R < ₃ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. A hydrogen atom in the organic group may be substituted with a fluorine atom. ]
A group represented by formula (2)

（２）

(2)

[In formula, R < ₄ > -R < ₈ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. A hydrogen atom in the organic group may be substituted with a fluorine atom. ]
Is at least one group selected from the group consisting of groups represented by:

  In one certain form, the said fluorine-containing solvent is a C6-C20 aromatic fluorine compound.

  In one certain form, the said composition for organic thin-film transistor insulating layers contains a fluororesin (C) further.

In one certain form, the said fluororesin (C) is at least 1 sort (s) of fluorine chosen from the group which consists of the fluororesin (C-1) defined below and the fluororesin (C-2) defined below. Resin.
Fluororesin (C-1):
Formula (3)

（３）

(3)

[In formula, X represents a C1-C20 monovalent organic group which has a fluorine atom, a fluorine atom, or a chlorine atom. ]
A repeating unit represented by formula (4)

（４）

(4)

[Wherein R ₉ represents an alkylene group. A hydrogen atom in the alkylene group may be substituted with a fluorine atom. ]
Fluororesin (C-2) containing a repeating unit represented by:
Formula (5)

（５）

(5)

[In formula, R < ₁₀ > -R < ₁₂ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. A hydrogen atom in the organic group may be substituted with a fluorine atom. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. Raa represents a C1-C20 divalent organic group. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom. a represents an integer of 0 to 20, and m represents an integer of 1 to 5. When there are a plurality of Raa, they may be the same or different. 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. And a second unit that contains two or more first functional groups, and the first functional group reacts with active hydrogen by irradiation of electromagnetic waves or heat. Fluororesin, a functional group that generates functional groups

  In one certain form, the said 1st functional group is at least 1 sort (s) of group chosen from the group which consists of the isocyanato group blocked with the blocking agent, and the isothiocyanate group blocked with the blocking agent.

  In one certain form, the said 1st functional group is a formula (6).

（６）

(6)

[Wherein, Xa represents an oxygen atom or a sulfur atom. R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

  In one certain form, the said 1st functional group is a formula (7).

（７）

(7)

[Wherein, Xb represents an oxygen atom or a sulfur atom. R ₁₅ , R ₁₆ and R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
It is group represented by these.

  Moreover, this invention provides the organic thin-film transistor which has a source electrode, a drain electrode, a gate electrode, an organic-semiconductor layer, and the insulating layer formed using one of the said compositions for organic thin-film transistor insulating layers.

  In one certain form, the said insulating layer is an overcoat insulating layer.

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

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

  The organic thin film transistor manufactured using the composition for an organic thin film transistor insulating layer of the present invention has a small absolute value of the threshold voltage when driven in the atmosphere.

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.

(Organic thin film transistor insulating composition)
<Compound (A)>
The compound (A) contained in the composition for an organic thin film transistor insulating layer of the present invention has a group having a cyclic ether structure. The cyclic ether structure refers to a structure in which carbon of a cyclic hydrocarbon is substituted with oxygen. The number of atoms forming the ring in the cyclic ether structure is preferably 10 or less, and more preferably 6 or less. The number of oxygen forming the ring in the cyclic ether structure is preferably 2 or less, and more preferably 1.

  The groups having a cyclic ether structure are subjected to an addition reaction with each other by ring opening by a cationic polymerization initiator that generates cations by heating or light irradiation. As a result, the compound (A) is polymerized to become a polymer, and a film showing high tensile strength is formed.

  The group having a cyclic ether structure is preferably at least one selected from the group consisting of a group represented by the formula (1) and a group represented by the formula (2). Among them, the group represented by the formula (2) is particularly preferable because it provides a film having excellent solvent resistance.

In formulas (1) and (2), R _{1 to} R ₈ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the organic group may be substituted with a fluorine atom.

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

  Examples of the monovalent organic group having 1 to 20 carbon atoms include a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and a cyclic hydrocarbon having 3 to 20 carbon atoms. Group, an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a linear hydrocarbon group having 1 to 6 carbon atoms, a branched hydrocarbon group having 3 to 6 carbon atoms, or 3 to 6 carbon atoms. These are cyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms.

  In the straight chain hydrocarbon group having 1 to 20 carbon atoms, the branched hydrocarbon group having 3 to 20 carbon atoms, and the cyclic hydrocarbon group having 3 to 20 carbon atoms, the hydrogen atoms contained in these groups are substituted with fluorine atoms. May be.

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

  Examples of the monovalent organic group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and tertiary butyl. Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl group, trifluoromethyl group, trifluoroethyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethyl group Phenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, methylanthryl group, ethylan Thrill group, pentafluoro Eniru group, trifluoromethylphenyl group, chlorophenyl group and a bromophenyl group.

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

  Examples of the group having a cyclic ether structure include a group having an epoxy structure and a group having an oxetane structure. The group having an oxetane structure includes a group having a 3-ethyloxetane structure.

  The part except the group having a cyclic structure of the compound (A) is a hydrogen atom or an organic group. The valence of the organic group is the number of groups having a cyclic ether structure contained in the compound (A). Examples of the organic group include a monovalent organic group having 1 to 20 carbon atoms and a divalent organic group having 1 to 20 carbon atoms.

Specific examples of the compound (A) include bis (3′-glycidyloxypropyl) -1,1,3,3-tetramethyldisiloxane, 3-ethyl-3- (2′-ethylhexyloxymethyl) -oxetane, 3-ethyl-3-{[(3-ethyl-oxetane-3-yl) methoxy] methyl} oxetane.

<Fluorine-containing solvent (B)>
The fluorine-containing solvent (B) contained in the composition for an organic thin film transistor insulating layer of the present invention can fluidize the compound (A) in the composition under normal environmental conditions used when producing an organic thin film transistor. And is an organic compound having a fluorine atom, which is volatilizable.

  When the fluorine-containing solvent (B) is contained in the organic thin film transistor insulating layer composition, the organic thin film transistor insulating layer composition is improved in the property of spreading as a thin film. Therefore, the insulating layer can be thinly formed by a coating method or a printing method, and the flatness of the formed insulating layer surface is improved.

  Furthermore, the organic compound having a fluorine atom has poor affinity with an organic substance having no fluorine atom, and the organic layer function of the organic compound having the fluorine atom constituting the organic thin film transistor or the organic compound having the fluorine atom is used. Does not adversely affect the interface of the organic layer.

  The fluorine-containing solvent is preferably composed of carbon, hydrogen and fluorine and does not contain any other atoms. This is because such an organic compound having a fluorine atom has particularly poor affinity with an organic substance having no fluorine atom.

  As the organic compound having a fluorine atom, an aromatic compound having a fluorine atom is preferably used. This is because the aromatic compound having a fluorine atom is excellent in the property of dissolving the compound (A).

  Among these, a preferred fluorine-containing solvent is an aromatic fluorine compound having 6 to 20 carbon atoms. Examples of the aromatic fluorine compound having 6 to 20 carbon atoms include hexafluorobenzene, pentafluorotoluene, octafluorotoluene, and tetrafluoroanisole. As a fluorine-containing solvent (B), you may use the solvent which added the leveling agent, surfactant, etc. as needed.

  In the composition for an organic thin film transistor insulating layer of the present invention, the content of the fluorine-containing solvent (B) is preferably 10 to 3000 parts by weight, preferably 100 parts by weight of the compound (A) containing a group having a cyclic ether structure. Is 15 to 2000 parts by weight. However, the content of the fluorine-containing solvent (B) is appropriately determined in consideration of the film thickness of the organic thin film transistor insulating layer to be formed and the type and amount of the resin used in combination in the composition for the organic thin film transistor insulating layer. Can be adjusted.

<Fluororesin (C)>
The composition for an organic thin film transistor insulating layer of the present invention may further contain a fluororesin (C). The fluororesin refers to an organic polymer having a structural unit containing a fluorine atom, for example, a repeating unit containing a fluorine atom.

  When the organic thin film transistor insulating layer material contains an organic compound containing a fluorine atom, the formed insulating layer has a low polarity and water repellency is enhanced.

  It is preferable that a fluororesin (C) has a functional group which can couple | bond with the atom of surfaces with high polarity, such as a glass surface and a metal surface. If it does so, the adhesiveness with respect to glass, a metal, etc. will improve the insulating layer containing a fluororesin (C).

<Fluororesin (C-1)>
An example of a preferable fluororesin (C) contains a hydroxyl group. For example, a fluororesin (C-1) containing a repeating unit represented by the formula (3) and a repeating unit represented by the formula (4) ).

（３）

(3)

（４）

(4)

In formula (3) showing the structure of the repeating unit contained in the fluororesin (C-1), X represents a monovalent organic group having 1 to 20 carbon atoms, a fluorine atom or a chlorine atom having a fluorine atom.
Examples of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a fluorophenyl group, and a pentafluorophenyl group.

  In one embodiment of the repeating unit represented by the formula (3), X is a chlorine atom.

In the formula (4) showing the structures of repeating units contained in the fluororesin (C-1), R ₉ represents an alkylene group. A hydrogen atom in the alkylene group may be substituted with a fluorine atom. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.

In one embodiment of the repeating unit represented by formula (4), R ₉ is a butylene group.

  The fluororesin (C-1) that can be used in the present invention is, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) and a raw material of the repeating unit that is represented by the formula (4). It can be produced by a method in which a polymerizable monomer is copolymerized using a photopolymerization initiator or a thermal polymerization initiator.

Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) include trifluoroethylene, 1,1,2-trifluoropropylene, and chlorotrifluoroethylene.
Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (4) include 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether.

  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 tar, benzyldiethyl ketal and diacetyl, anthraquinone derivatives such as methylanthraquinone and chloroanthraquinone, thioxanthone derivatives such as chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, and sulfur compounds such as diphenyl disulfide and dithiocarbamate. It is done.

  The thermal polymerization initiator may be any radical polymerization initiator, such as 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 peroxide Diacyl peroxides such as o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, tert -Hydroperoxides such as butyl peroxide, dialkyl peroxides such as dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, and trialkyls such as tris (tert-butylperoxy) triazine Peroxyketals such as peroxides, 1,1-di-tert-butylperoxycyclohexane, 2,2-di (tert-butylperoxy) butane, tert-butylperoxypivalate, tert-butyl Luperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3,5,5 Alkyl peresters such as trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, di-tert-butylperoxytrimethyladipate, diisopropyl peroxydicarbonate, di-sec-butylperoxydi Examples thereof include peroxycarbonates such as carbonate and tert-butylperoxyisopropyl carbonate.

  The fluororesin (C-1) that can be used in the present invention is a polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) and a polymerizability that is a raw material of the repeating unit represented by the formula (4). Other polymerizable monomers other than the monomer may be added during the polymerization.

  Examples of the other polymerizable monomers include unsaturated hydrocarbons and derivatives thereof, and vinyl ether derivatives.

  The kind of the other polymerizable monomer is appropriately selected according to the characteristics required for an insulating layer such as an overcoat insulating layer. Another preferred form of the polymerizable monomer is a monomer having no active hydrogen-containing group such as an alkyl group.

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

  Examples of vinyl ether derivatives include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether and the like.

  Of these, butyl vinyl ether and cyclohexyl vinyl ether are preferable.

  The amount of the polymerizable monomer used as the raw material of the repeating unit represented by the formula (3) is adjusted so that the amount of fluorine introduced into the fluororesin (C-1) becomes an appropriate amount.

  Examples of the fluororesin (C-1) that can be used in the present invention include poly (trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-ethyl vinyl ether), poly (trifluoroethylene-co-4-hydroxybutyl vinyl ether). -Co-butyl vinyl ether), poly (trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-3-chloromethylphenyl vinyl ether), poly (trifluoroethylene-co-4-hydroxybutyl vinyl ether-co-vinyl cinnamate ) And the like.

<Fluororesin (C-2)>
Another example of a preferable fluororesin (C) contains a functional group that reacts with active hydrogen. For example, the fluororesin (C) contains a repeating unit represented by the formula (5), and the first functional group is 2 The fluororesin (C-2) is a functional group that contains two or more and the first functional group generates a second functional group that reacts with active hydrogen by the action of electromagnetic waves or heat.

（５）

(5)

In formula (5) showing the structure of the repeating unit contained in the fluororesin (C-2), R _{10 to} R ₁₂ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. . R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. Raa represents a C1-C20 divalent organic group. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom. a represents an integer of 0 to 20, and m represents an integer of 1 to 5. When there are a plurality of Raa, they may be the same or different. 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.

  The divalent organic group having 1 to 20 carbon atoms may be linear, branched or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, a nitrogen atom, Hetero atoms such as oxygen atoms and sulfur atoms may be contained. For example, a C1-C20 divalent linear aliphatic hydrocarbon group, a C3-C20 divalent branched aliphatic hydrocarbon group, a C3-C20 divalent cyclic aliphatic carbonization A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with a hydrogen group, an alkyl group or the like, -O-CO-, -O-, -CO-NH-, -NH-CO-NH -, -NH-CO-O-. These groups may have a substituent. Among them, a divalent linear hydrocarbon group having 1 to 6 carbon atoms, a divalent branched hydrocarbon group having 3 to 6 carbon atoms, a divalent cyclic hydrocarbon group having 3 to 6 carbon atoms, an alkyl group, etc. A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with —O—CO— is preferable.

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

  Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent include a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, and a diethylenephenylene group. , Triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, ethylanthrylene group, etc. Is mentioned.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R _{10 to} R ₁₂ include the same groups as those of the monovalent organic group having 1 to 20 carbon atoms represented by R _1. . Examples of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by Rf are the same as those of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by X. Groups.

  Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R include, for example, a linear hydrocarbon group having 1 to 20 carbon atoms, a branched hydrocarbon group having 3 to 20 carbon atoms, and 3 to 3 carbon atoms. 20 cyclic hydrocarbon groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably linear hydrocarbon groups having 1 to 6 carbon atoms, branched hydrocarbon groups having 3 to 6 carbon atoms, It is a C3-C6 cyclic hydrocarbon group and a C6-C20 aromatic hydrocarbon group.

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

  Examples of the monovalent organic group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and tertiary butyl. Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexynyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group , Diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, methylanthryl group, ethylanthryl group, chlorophenyl group, bromophenyl group, etc. Is mentioned.

In one embodiment of the repeating unit represented by the formula (5), R _{10 to} R ₁₂ are hydrogen atoms, Rf is a fluorine atom, a is 0, and m is 5.

The fluororesin (C-2) that may be used in the present invention contains the repeating unit represented by the formula (5) and contains two or more first functional groups, and the first functional group However, it contains a functional group that generates a second functional group that reacts with active hydrogen by the irradiation of electromagnetic waves or the action of heat.
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 that reacts with active hydrogen is preferably protected (blocked) until heat is applied in the step of forming the gate insulating layer. In other words, the first functional group is preferably deprotected by heat to generate a second functional group that reacts with active hydrogen.
This is because the storage stability of the composition is improved.

Examples of the first functional group include an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent.
The isocyanate group blocked with the blocking agent or the blocked isothiocyanate group is a blocking agent having only one active hydrogen capable of reacting with an isocyanato group or an isothiocyanate group in one molecule of the blocking agent, an isocyanato group or an isothiocyanato group. It can be produced by reacting with a group.

  The blocking agent preferably dissociates at a temperature of 170 ° C. or lower even 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. These blocking agents may be used alone or in combination of two or more. Preferable blocking agents include oxime compounds and pyrazole compounds.

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

  The isocyanato group blocked with a blocking agent that may be used in the present invention is a group represented by the formula (6), a group in which Xa is an oxygen atom, a group represented by the formula (7), A group in which Xb is an oxygen atom is preferable. The isothiocyanato group blocked with a blocking agent that may be used in the present invention is a group represented by the formula (6), wherein Xa is a sulfur atom, or a group represented by the formula (7). A group in which Xb is a sulfur atom is preferred.

（６） （７）

(6) (7)

In Formula (6), Xa represents an oxygen atom or a sulfur atom, and R ₁₃ and R ₁₄ each independently represent 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 ₁₃ and R ₁₄ include the same groups as the examples of the monovalent organic group represented by R _{10 to} R ₁₂ .
In one embodiment of the repeating unit represented by the formula (6), Xa is an oxygen atom, R ₁₃ is a methyl group, and R ₁₄ is an ethyl group.

In Formula (7), Xb represents an oxygen atom or a sulfur atom, and R ₁₅ , R ₁₆ and R ₁₇ each independently represent 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 ₁₅ , R ₁₆ and R ₁₇ include the same groups as those of the monovalent organic group represented by R _{10 to} R _12. .
In one embodiment of the repeating unit represented by the formula (7), Xb is an oxygen atom, and R _{15 to} R ₁₇ are hydrogen atoms.

  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) And 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, (N-3-ethyl-5-propylpyrazolylthiocarbonyl) amino group.
The first functional group used in the present invention is preferably an isocyanato group blocked with a blocking agent.

Next, the manufacturing method of the fluororesin (C-2) used for this invention is demonstrated. The fluororesin (C-2) is obtained by, for example, converting a polymerizable monomer that is a raw material of the repeating unit represented by the formula (5) and a polymerizable monomer containing the first functional group into a photopolymerization initiator or heat. It can manufacture by the method of copolymerizing using a polymerization initiator.
Examples of the photopolymerization initiator and the thermal polymerization initiator include the same photopolymerization initiator and thermal polymerization initiator that can be used in the production of the fluororesin (C-1).

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (5) include 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, 2,3,4,5,6. -Pentafluorostyrene, 4-fluoromethylstyrene, etc. are mentioned.

  Examples of the polymerizable monomer containing the first functional group include an isocyanato group blocked with a blocking agent or a monomer having an isothiocyanate group blocked with a blocking agent and an unsaturated bond. A monomer having an isocyanato group blocked with the blocking agent or an isothiocyanate group blocked with a blocking agent and an unsaturated bond includes an isocyanate group or a compound having an isothiocyanato group and an unsaturated bond, and a blocking agent. It can be produced by reacting. As the unsaturated bond, an unsaturated double bond is preferable.

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

  As the blocking agent, the above blocking agents can be preferably used. In the production of a monomer having an isocyanato group blocked with a blocking agent or an isothiocyanato group blocked with a blocking agent and an unsaturated bond, an organic solvent, a catalyst, or the like may be added as necessary.

  As the monomer having an unsaturated double bond and an isocyanate group blocked with a blocking agent, 2- [O- [1′-methylpropylideneamino] carboxyamino] ethyl-methacrylate, 2- [N- [1 ', 3'-dimethylpyrazolyl] carboxyamino] ethyl-methacrylate, 2- [O- [1'-methylpropylideneamino] thiocarboxyamino] ethyl-methacrylate, 2- [N- [1', 3'-dimethyl] Pyrazolyl] thiocarboxyamino] ethyl-methacrylate and the like.

  The fluororesin (C-2) that can be used in the present invention is a polymerization monomer other than the polymerizable monomer that is a raw material of the repeating unit represented by the formula (5) and the polymerizable monomer containing the first functional group. A monomer capable of being added may be added during the polymerization.

  Examples of the other polymerizable monomers include acrylic acid esters and derivatives thereof, methacrylic acid esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof, organic Vinyl esters of carboxylic acids and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, dialkyl esters of fumaric acid and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, organic carboxylic acids Examples include N-vinylamide derivatives, maleimides and derivatives thereof, terminal unsaturated hydrocarbons and derivatives thereof, and unsaturated bond-containing organic germanium compounds.

The kind of the other polymerizable monomer is appropriately selected according to the characteristics required for the insulating layer. From the viewpoint of excellent durability and low hysteresis of the organic thin film transistor, a monomer that has a high molecular density and forms a hard film such as styrene or a styrene derivative is selected.
In addition, from the viewpoint of adhesion to the adjacent surface of the insulating layer such as the gate electrode or the surface of the substrate, monomers that impart flexibility such as methacrylic acid esters and derivatives thereof, acrylic acid esters and derivatives thereof are selected. The In a preferred embodiment, a monomer that does not have an active hydrogen-containing group such as an alkyl group such as a methyl group or an ethyl group is selected.

  For example, by using a fluororesin polymerized by combining a polymerizable monomer as a raw material of the repeating unit represented by the formula (5) and styrene or a styrene derivative having no active hydrogen-containing group in the composition for an organic thin film transistor insulating layer. In particular, a gate insulating layer having high durability and low hysteresis can be obtained.

  As the acrylates and derivatives thereof, monofunctional acrylates and polyfunctional acrylates can be used although there are restrictions on the amount used. For example, methyl acrylate, ethyl acrylate, acrylic acid- n-propyl, isopropyl acrylate, acrylate-n-butyl, isobutyl acrylate, acrylate-sec-butyl, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, acrylic Cyclohexyl acid, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyphenyl acrylate ethyl, Tylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, N, N- Dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl Acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohe Sil-2-hydroxypropyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) Ethyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypro Pyracrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H- Examples thereof include 1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate and the like.

  As the methacrylic acid esters and derivatives thereof, monofunctional methacrylates and polyfunctional methacrylates can be used although there are restrictions on the amount used, for example, methyl methacrylate, methacrylic acid Ethyl, methacrylate-n-propyl, isopropyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-sec-butyl, hexyl methacrylate, octyl methacrylate, methacrylate- 2-ethylhexyl, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid -3-hydroxy group Pill, 2-hydroxybutyl methacrylate, 2-hydroxyphenylethyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-acryloylmorpholine, 2,2 , 2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl Acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate , 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl)- 2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- (perful Oro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 1H , 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H- Examples thereof include 1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, and the like.

  Examples of styrene and derivatives thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, and 3,4-dimethyl. Styrene, 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-hydroxystyrene, 2-vinylbiphenyl, 3-vinyl Biphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p- Isopropenyltoluene, 2,4-dimethyl-α-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene , Α-chlorostyrene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, 4-aminostyrene and the like.

  Examples of acrylonitrile and its derivatives include acrylonitrile. Examples of methacrylonitrile and derivatives thereof include methacrylonitrile.

  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.

  Dialkyl esters of fumaric acid and derivatives thereof include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate And dibenzyl fumarate.

  Dialkyl esters of maleic acid and derivatives thereof include dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate And dibenzyl maleate.

  Dialkyl esters of itaconic acid and derivatives thereof include dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate And dibenzyl itaconate.

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

  Examples of maleimide and derivatives thereof include N-phenylmaleimide and N-cyclohexylmaleimide.

  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 unsaturated bond-containing organic germanium compound include allyltrimethylgermanium, allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, triethylvinylgermanium, and the like.

  Among these, acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, acrylonitrile, methacrylonitrile, and allyltrimethylgermanium are preferable.

  The amount of fluorine introduced into the fluororesin (C) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and further preferably 5 to 40% by mass with respect to the mass of the polymer compound. . If the amount of fluorine is less than 1% by mass or more than 60% by mass, the compatibility with the fluorinated solvent (B) may deteriorate and it may be difficult to prepare a composition.

  The fluororesin (C) is preferably a polymer compound having a weight average molecular weight of 3000 to 1000000, more preferably 5000 to 500000. The fluororesin (C) may be linear, branched or cyclic.

<Cationic polymerization initiator>
It is preferable to add a photocationic polymerization initiator or a thermal cationic polymerization initiator to the composition for an organic thin film transistor insulating layer of the present invention. This is because the ring-opening addition reaction of the cyclic ether structure contained in the compound (A) easily proceeds.

  Examples of the photo cationic polymerization initiator and the thermal cationic polymerization initiator include iodonium salts and sulfonium salts.

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

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

  Specific examples of the photocationic polymerization initiator include trade name Rhodosil 2074 (manufactured by Rhodia Japan), trade name Adekaoptoma-SP-150 (made by ADEKA), trade name Adekaoptoma-SP-152 (ADEKA Corporation). Product name) ADEKA OPTOMA-SP-170 (manufactured by ADEKA Corporation), trade name ADEKA OPTOMA-SP-172 (manufactured by ADEKA Corporation), and the like. Also, sulfonium salt compounds described in JP-A-9-118663 can be used.

  Specific examples of the thermal cationic polymerization initiator include trade name Adeka Opton CP series (manufactured by ADEKA Corporation).

  The ratio of the photocationic polymerization initiator or the thermal cationic polymerization initiator in the composition for an organic thin film transistor insulating layer of the present invention is 100 parts by weight of the compound (A) containing a group having a cyclic ether structure. The range of 0.0001-30 weight part is preferable, More preferably, it is 0.001-10 weight part. Further, two or more kinds of the cationic photopolymerization initiator or the thermal cationic polymerization initiator may be used.

  Organic thin-film transistor insulating layer of the present invention by mixing the compound (A) containing a group having a cyclic ether structure, a fluorine-containing solvent (B), and if necessary, a fluororesin (C) and a cationic polymerization initiator The composition for use is obtained.

  When the fluororesin (C) is contained in the composition for an organic thin film transistor insulating layer of the present invention, the content thereof is 600 parts by weight or less, preferably 100 to 500 parts by weight with respect to 100 parts by weight of the compound (A). is there.

  When content of the fluororesin (C) in the composition for organic thin-film transistor insulating layers exceeds 600 weight part with respect to 100 weight part of compounds (A), the solvent resistance of an organic thin-film transistor insulating layer may fall.

  When only the fluororesin (C-1) having a hydroxyl group is used as the fluororesin (C), the content of the fluororesin (C-1) in the composition for an organic thin film transistor insulating layer of the present invention is the compound ( A) It is 50-600 weight part with respect to 100 weight part, Preferably it is 100-500 weight part, More preferably, it is 200-400 weight part.

  When the content of the fluororesin (C-1) in the composition for an organic thin film transistor insulating layer is less than 50 parts by weight with respect to 100 parts by weight of the compound (A), the coating film may agglomerate during drying, and 600 When it exceeds the weight part, the solvent resistance of the organic thin film transistor insulating layer may be lowered.

  In this case, the content of the fluorine-containing solvent (B) in the composition for an organic thin film transistor insulating layer is 100 to 3000 parts by weight, preferably 500 to 2000 parts by weight, based on 100 parts by weight of the compound (A). Preferably it is 800-1500 weight part.

  When the content of the fluorine-containing solvent (B) in the composition for an organic thin film transistor insulating layer is less than 100 parts by weight with respect to 100 parts by weight of the compound (A), the flatness of the coating film may be deteriorated. When it exceeds the part, the film quality of the coating film is deteriorated, and pinholes may be generated in the organic thin film transistor insulating layer.

  As a fluororesin (C), you may mix and use the fluororesin (C-1) which has a hydroxyl group, and the fluororesin (C-2) containing the functional group which reacts with active hydrogen. Since the functional groups contained in the fluororesin (C-1) and the fluororesin (C-2) react with each other to form a crosslinked structure inside the organic thin film transistor insulating layer, polarization of the insulating layer is suppressed, Increases solvent resistance.

  The composition for organic thin-film transistor insulating layers of this invention is a composition used for formation of the insulating layer contained in an organic thin-film transistor. As a composition for organic thin-film transistor insulating layers, the composition for organic thin-film transistor overcoat layers used for formation of an overcoat layer and the composition for organic thin-film transistor gate insulating layers used for formation of a gate insulating layer are mentioned. The organic thin film transistor insulating layer composition is preferably used for forming an overcoat layer of an organic thin film transistor.

  The overcoat layer formed using the composition for an organic thin film transistor insulating layer of the present invention is excellent in insulation and airtightness. Therefore, the organic thin film transistor having the overcoat layer can be driven stably in the atmosphere because the organic semiconductor compound contained in the transistor is effectively cut off from the surrounding environment.

(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 insulating layer 7 covering the entire element are provided.

  A bottom gate top contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, an organic semiconductor layer formed on the gate insulating layer, and a source electrode formed on the organic semiconductor layer. It can be manufactured by forming a drain electrode and forming an overcoat insulating layer.

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

  A bottom gate bottom contact type organic thin film transistor includes, for example, a gate electrode formed on a substrate, a gate insulating layer formed on the gate electrode, a source electrode and a drain electrode formed on the gate insulating layer, and a source electrode and a drain electrode. It can be manufactured by forming an organic semiconductor layer thereon and forming an overcoat insulating layer.

  The overcoat insulating layer is formed by applying, drying and curing the overcoat insulating layer composition of the present invention on the organic semiconductor layer.

  The overcoat insulating layer composition can be applied onto the organic semiconductor layer by known spin coating, die coating, screen printing, inkjet, or the like.

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

As organic semiconductor compounds, π-conjugated polymers are widely used. For example, polypyrroles, polythiophenes, polyanilines, polyallylamines, fluorenes, polycarbazoles, polyindoles, poly (p-phenylene vinylene) s are used. Can do.
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 Can be used. Specific examples include condensates of 9,9-di-n-octylfluorene-2,7-di (ethylene boronate) and 5,5′-dibromo-2,2′-bithiophene. .

  The organic semiconductor layer is formed by, for example, adding an organic semiconductor coating solution by adding a solvent or the like if necessary for the organic semiconductor compound, and applying and drying this on the gate insulating layer.

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

  By using the organic thin film transistor of the present invention, a display member having an organic thin film transistor can be suitably produced. Using a display member having the organic thin film transistor, a display including the display member can be suitably produced.

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

Synthesis example 1
(Synthesis of polymer compound 1)
Under an inert atmosphere, 5.7 g of 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene, bis (4-bromophenyl)-(4-secondarybutylphenyl) -4.50 g of amine, 2.2 mg of palladium acetate, 15.1 mg of tri (2-methylphenyl) phosphine, methyltrioctylammonium chloride (manufactured by Aldrich, trade name “Aliquat® 336”) 91 g and 70 ml of toluene were mixed and heated to 105 ° C. 19 ml of 2 mol / kg sodium carbonate aqueous solution was added dropwise to the reaction solution, and the mixture was refluxed for 4 hours. Thereafter, 121 mg of phenylboric acid was added, and the mixture was further refluxed for 3 hours. Next, a sodium diethyldithiacarbamate aqueous solution was added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (60 ml), 3 times with a 3 wt% aqueous acetic acid solution (60 ml) and 3 times with water (60 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was dropped into methanol (3 L) and stirred for 3 hours, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound 1 represented by the following formula was 5.25 g. Here, n in the following formula represents the degree of polymerization.

高分子化合物１

Polymer compound 1

The weight average molecular weight calculated | required from the standard polystyrene of the high molecular compound 1 was 2.6 * 10 < ⁵ >. The measurement conditions of the weight average molecular weight were apparatus: GPC manufactured by Shimadzu, column: one “Tskel super HM-H” + one “Tskel super H2000”, and mobile phase: THF.

Synthesis example 2
(Synthesis of polymer compound 2)
2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 2.00 g, 2,2′-azobis (2-methylpropionitrile) 0.01 g, 2,3,4,5,6-penta Put 3.00 g of fluorotoluene (manufactured by Wako Pure Chemical Industries, Ltd.) into a 50 ml pressure vessel (manufactured by Ace), bubble with argon, seal tightly, and polymerize in an oil bath at 60 ° C. for 24 hours. A 2,3,4,5,6-pentafluorotoluene solution of polymer compound 2 was obtained. Here, n in the following formula represents the degree of polymerization.

高分子化合物２

Polymer compound 2

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 2 was 88,000. The conditions for measuring the weight average molecular weight were the same as those described in Synthesis Example 1.

Example 1
(Preparation of Composition 1 for Organic Thin Film Transistor Insulating Layer)
In a 20 ml sample bottle, 2.00 g of 2,3,4,5,6-pentafluorotoluene solution containing 40% by weight of “Lumiflon (registered trademark) LF200F” (manufactured by Asahi Glass Co., Ltd., OH value 45 mgKOH / g) 0.27 g of “Aron Oxetane (registered trademark) OXT-221” (manufactured by Toagosei Co., Ltd.), 0.00054 g of “Lordsil (registered trademark) 2074” (manufactured by Rhodia Japan Ltd.), 2,3,4,5,6- 2.00 g of pentafluorotoluene (manufactured by Wako Pure Chemical Industries, Ltd.) was added and mixed to prepare a solution. The obtained solution was filtered through a membrane filter having a pore diameter of 0.45 μm to prepare an organic thin film transistor insulating layer composition 1.

  “Aron oxetane (registered trademark) OXT-221” is a compound having a structure represented by the following formula.

“Lumiflon (registered trademark) LF200F” is a polymer compound having a repeating unit represented by the formula (2-a) and a repeating unit represented by the formula (3-a). In formula (2-a), X represents a fluorine atom, a chlorine atom or a trifluoromethyl group. In formula (3-a), R ₄ represents an alkylene group.

（２−ａ） （３−ａ）

(2-a) (3-a)

(Production of field-effect organic thin-film transistors)
Polymer compound 1 was dissolved in xylene to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and the solution was filtered through a membrane filter having a pore size of 0.45 μm to prepare a coating solution. .

The obtained coating solution containing the polymer compound 1 is applied on a bottom gate bottom contact element (manufactured by Kyodo Inter) by a spin coating method and dried in nitrogen at 200 ° C. for 10 minutes to obtain an active layer having a thickness of about 60 nm. Formed.
Subsequently, the composition 1 for organic thin-film transistor insulating layers was apply | coated by the spin coat method on the obtained active layer. Then, it dried at 50 degreeC for 5 minutes, and irradiated with the ultraviolet-ray (254 nm) for 1 minute using UV / ozone cleaner (Model UV-1, the Samco make) in argon. Thereafter, the film was baked at 100 ° C. for 30 minutes to form an overcoat insulating layer having a thickness of about 4 μm, and a field effect organic thin film transistor 1 was produced.

<Transistor characteristics>
About the produced field effect type organic thin-film transistor 1, the transistor characteristic was measured in air | atmosphere. Under the condition that the gate voltage Vg was changed to 20 to -40 V and the source-drain voltage Vsd was changed to 0 to -40 V, the transistor characteristics were changed to a vacuum probe (BCT22MDC-5-HT-SCU; Nagase Electronic Equipments Service Co. Ltd.) and measured in the air. Table 1 shows the measured threshold voltage (Vth).

Comparative Example 1
(Production of field-effect organic thin-film transistors)
Instead of the composition 1 for an organic thin film transistor insulating layer, 1 part of 2,3,4,5,6-pentafluorotoluene is added to 1.00 g of a 2,3,4,5,6-pentafluorotoluene solution of the polymer compound 2. A field effect organic thin film transistor was produced in the same manner as in Example 1 except that 0.000 g was added and the composition 2 for an organic thin film transistor insulating layer prepared by filtering through a membrane filter having a pore diameter of 0.45 μm was used. The transistor characteristics were measured. The thickness of the overcoat insulating layer was about 6 μm. The absolute value of the threshold voltage was 40 V or more, and the device was not driven under the conditions where the gate voltage Vg was changed to 20 to -40 V and the source-drain voltage Vsd was changed to 0 to -40 V.

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

Claims (10)

An organic thin film transistor insulating layer composition comprising a compound (A) containing a group having a cyclic ether structure and a fluorine-containing solvent (B) ,
The composition for organic thin-film transistor insulating layers whose this fluorine-containing solvent is a C6-C20 aromatic fluorine compound . An organic thin film transistor insulating layer composition comprising a compound (A) containing a group having a cyclic ether structure, a fluorinated solvent (B), and a fluororesin (C),
Organic thin film transistor insulation wherein the fluororesin (C) is at least one fluororesin selected from the group consisting of a fluororesin (C-1) defined below and a fluororesin (C-2) defined below Layer composition.
Fluororesin (C-1):
Formula (3)

(3)
[In formula, X represents a C1-C20 monovalent organic group which has a fluorine atom, a fluorine atom, or a chlorine atom. ]
A repeating unit represented by formula (4)

(4)
[Wherein R ₉ represents an alkylene group. A hydrogen atom in the alkylene group may be substituted with a fluorine atom. ]
Fluororesin (C-2) containing a repeating unit represented by:
Formula (5)

(5)
[In formula, R < ₁₀ > -R < ₁₂ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. Raa represents a C1-C20 divalent organic group. A hydrogen atom in the divalent organic group may be substituted with a fluorine atom. a represents an integer of 0 to 20, and m represents an integer of 1 to 5. When there are a plurality of Raa, they may be the same or different. 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. And a second functional group containing two or more first functional groups, the first functional group reacting with active hydrogen by the action of electromagnetic waves or heat. Fluororesin, a functional group that produces A group having a cyclic ether structure is represented by the formula (1)

(1)
[In formula, R < ₁ > -R < ₃ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. A hydrogen atom in the organic group may be substituted with a fluorine atom. ]
A group represented by formula (2)

(2)
[In formula, R < ₄ > -R < ₈ > represents a hydrogen atom or a C1-C20 monovalent organic group each independently. A hydrogen atom in the organic group may be substituted with a fluorine atom. ]
The composition for organic thin-film transistor insulating layers according to claim 1 or 2 , which is at least one group selected from the group consisting of groups represented by formula ( 1 ). 3. The organic thin film transistor insulating layer according to claim 2 , wherein the first functional group is at least one group selected from the group consisting of an isocyanato group blocked with a blocking agent and an isothiocyanato group blocked with a blocking agent. Composition. The first functional group has the formula (6)

(6)
[Wherein, Xa represents an oxygen atom or a sulfur atom. R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The composition for an organic thin film transistor insulating layer according to claim 2 , which is a group represented by the formula: The first functional group has the formula (7)

(7)
[Wherein, Xb represents an oxygen atom or a sulfur atom. R ₁₅ , R ₁₆ and R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]
The composition for an organic thin film transistor insulating layer according to claim 2 , which is a group represented by the formula: The organic thin-film transistor which has a source electrode, a drain electrode, a gate electrode, an organic-semiconductor layer, and the insulating layer formed using the composition for organic thin-film transistor insulating layers as described in any one of Claims 1-6 . The organic thin film transistor according to claim 7 , wherein the insulating layer is an overcoat insulating layer. The display member containing the organic thin-film transistor of Claim 7 or 8 . A display comprising the display member according to claim 9 .

Images