WO2013031820A1 - Organic thin film transistor insulating layer material - Google Patents

Abstract

The present invention relates to an organic thin film transistor insulating layer material with which an organic thin film transistor having a low hysteresis and threshold voltage may be manufactured. The organic thin film transistor insulating layer material of the present invention comprises (A) a high molecular compound which contains a benzyl thiocarbamate group (-Ph-CH₂-SCSNR₂) in a molecule, and (B) an unsaturated double bond compound which contains at least two unsaturated double bonds in the molecule.

Description

Organic thin film transistor insulating layer material

The present invention relates to a material suitable for forming an insulating layer of an organic thin film transistor.

Since organic thin film transistors can be manufactured at a lower temperature than inorganic semiconductors, plastic substrates and films can be used as the substrate, and by using such a substrate, a flexible, lightweight and hardly breakable element 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.

Furthermore, since there are a wide variety of materials that can be used for the study of transistors, if materials having different molecular structures are used for the study, elements having a wide range of characteristic variations 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 on / off of a drain current. Therefore, a gate insulating layer is formed between the gate electrode and the semiconductor layer.

Further, the organic semiconductor compound used for forming the organic semiconductor layer of the field effect organic thin film transistor is easily affected by the 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 element structure of the bottom gate type organic thin film transistor which is one type of field effect type organic thin film transistor in which the organic semiconductor compound is exposed, an overcoat insulating layer covering the entire element is formed to remove the organic semiconductor compound from contact with the outside air. It is essential to protect. On the other hand, in the top gate type organic thin film transistor device structure, the organic semiconductor compound is coated and protected by a gate insulating layer.

Thus, an insulating layer material is used to form an overcoat insulating layer, a gate insulating layer, and the like that cover the organic semiconductor layer in the organic thin film transistor. 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. A material used for forming the organic thin film transistor insulating layer is referred to as an organic thin film transistor insulating layer material.

The organic thin film transistor insulating layer material is required to have excellent insulating properties and excellent dielectric breakdown strength when formed into a thin film. In particular, in a bottom gate type field effect organic thin film transistor, an organic semiconductor layer is formed so as to overlap with a gate insulating layer. Therefore, the organic thin film transistor gate insulating layer material has an affinity with an organic semiconductor compound for forming an interface in close contact with the organic semiconductor layer, and the surface of the film formed from the organic thin film transistor gate insulating layer material on the organic semiconductor layer side. It is required to be flat.

As a technology that meets such a requirement, Patent Document 1 describes that an epoxy resin and a silane coupling agent are used in combination as an organic thin film transistor gate insulating layer material. In this technique, a hydroxyl group produced during the curing reaction of an epoxy resin is reacted with a silane coupling agent. This is because the hydroxyl group enhances the hygroscopicity of the gate insulating layer material and impairs the stability of the transistor performance.

Non-Patent Document 1 describes that a resin obtained by thermally cross-linking polyvinylphenol and a melamine compound is used for the gate insulating layer. In this technique, the hydroxyl group contained in polyvinylphenol is removed by crosslinking with a melamine compound, and at the same time the film strength is increased. The pentacene TFT having this gate insulating layer has a small hysteresis and exhibits durability against gate bias stress.

Non-Patent Document 2 describes that polyvinyl gate and a copolymer obtained by copolymerizing vinyl phenol and methyl methacrylate are used for the gate insulating layer. In this technique, the hydroxyl group of vinylphenol interacts with the carbonyl group of methyl methacrylate to reduce the polarity of the entire film. The pentacene TFT having this gate insulating layer has a small hysteresis and exhibits stable electrical characteristics.

However, in consideration of practical use of a light-emitting element such as an organic electroluminescence element (organic EL element), it is necessary to further improve the operation accuracy of the organic thin film transistor. The organic thin film transistor having the conventional gate insulating layer has a threshold voltage ( The absolute value and hysteresis of Vth) are large.

On the other hand, benzyldiethyldithiocarbamate (Ph-CH ₂ -SCSNEt ₂ ), a kind of iniferter, dissociates the bond between benzyl carbon and sulfur reversibly when irradiated with ultraviolet light, and the benzyl radical (Ph-CH _2. ) And diethyldithiocarbamyl radical (.SCSNEt ₂ ). In addition, the bond between benzyl carbon and sulfur is reversibly dissociated by heat. The benzyl radical functions as a polymerization initiator for the vinyl monomer, and the diethyldithiocarbamyl radical caps the polymerization terminal. Therefore, radical polymerization can proceed to many monomers in a living manner by selecting irradiation conditions (intensity, time) and solution conditions (monomer concentration, monomer / initiator ratio).

JP 2007-305950 A

An object of the present invention is to provide an organic thin film transistor insulating layer material capable of producing an organic thin film transistor having a small absolute value of threshold voltage and small hysteresis.

In view of the above, the absolute value and hysteresis of the threshold voltage (Vth) of the organic thin film transistor can be reduced by forming the gate insulating layer using a specific resin composition capable of forming a crosslinked structure.

That is, the present invention has the formula (1)

(1)

[Wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. a represents an integer of 0 or 1, and n represents an integer of 1 to 5. When there are a plurality of R ₂ , they may be the same or different. When there are a plurality of R ₃ , they may be the same or different. When there are a plurality of R, they may be the same or different. ]
A high molecular compound (A) containing a repeating unit represented by the formula (A) and a double bond compound (B) which is a double bond compound containing two or more double bonds and is different from the high molecular compound (A) The organic thin-film transistor insulating-layer material containing is provided.

In one certain form, the said double bond compound (B) is a low molecular double bond compound (B-1) containing two or more double bonds, and two repeating units containing a double bond. It is at least one selected from the group consisting of the polymer double bond compound (B-2) contained above.

In one embodiment, the low molecular double bond compound (B-1) is represented by the formula (2)

(2)

[Wherein, R ₄ and R ₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ]
The low molecular double bond compound containing the bivalent organic group represented by these, and two or more double bonds.

In one embodiment, the low molecular double bond compound (B-1) is represented by the formula (5)

(5)

[Wherein R ₈ to R ₁₂ and R ₁₇ to R ₂₁ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R ₁₃ to R ₁₆ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _dd , R _ee and R _ff each independently represents a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. p1, p2 and p3 each independently represents an integer of 0 or 1. ]
It is a low molecular double bond compound represented by these.

In one embodiment, the polymer double bond compound (B-2) has the formula (3)

(3)

[Wherein R ₆ represents a hydrogen atom or a methyl group. R _bb represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. b represents an integer of 0 or 1. ]
A repeating unit represented by formula (4):

(4)

[Wherein, R ₇ represents a hydrogen atom or a methyl group. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _cc represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. c represents an integer of 0 or 1. m represents an integer of 1 to 5. When there are a plurality of R ′, they may be the same or different. ]
It is a polymeric double bond compound containing the at least 1 sort (s) of repeating unit chosen from the group which consists of a repeating unit represented by these.

The present invention also provides an organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material.

In one embodiment, the organic thin film transistor insulating layer is a gate insulating layer.

The present invention also provides a display member comprising the organic thin film transistor.

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

An organic thin film transistor having an insulating layer formed using the organic thin film transistor insulating layer material of the present invention has a low absolute value of threshold voltage and low hysteresis.

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.

In the present specification, “polymer compound” refers to a compound having a structure in which a plurality of the same structural units are repeated in the molecule, and includes a so-called dimer.

The organic thin film transistor insulating layer material of the present invention includes a polymer compound (A) containing a dithiocarbamylmethylphenyl group (—Ph—CH ₂ —SCSNR ₂ R ₃ ) substituted with R ₂ and R ₃ , It is characterized by containing a binding compound (B). Since the dithiocarbamylmethylphenyl group in the polymer compound (A) and the double bond in the double bond compound (B) react in a living manner, a cured film having a high crosslinking density is formed. When the crosslink density of the organic thin film transistor insulating layer is increased, the movement of the molecular structure is suppressed, and the polarization of the insulating layer is suppressed. When the polarization of the insulating layer is suppressed, for example, when used as a gate insulating layer, the absolute value of the threshold voltage of the organic thin film transistor is lowered, and the operation accuracy is improved.

<Polymer Compound (A)>
The polymer compound (A) is, for example, a polymer compound having a repeating unit represented by the above formula (1).

In formula (1), R ₁ represents a hydrogen atom or a methyl group. In one certain form, R < ₁ > is a hydrogen atom.

In the formula (1), R represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.

By introducing fluorine into the organic thin film transistor insulating layer material, the gate insulating layer formed from the material has low polarity, and there are few components that are easily polarized even when a gate voltage is applied, and the polarization of the gate insulating layer is suppressed. Is done.

On the other hand, in the organic thin film transistor insulating layer material of the present invention, fluorine atoms are not an essential component. The surface of the organic thin film transistor insulating layer containing no fluorine is excellent in affinity with an organic material. As a result, for example, when the organic semiconductor layer is formed adjacent to the organic thin film transistor insulating layer, the adhesion between the two becomes good. In that case, the flatness of the surface of the formed organic semiconductor layer is improved.

In addition, since the organic thin film transistor insulating layer material does not contain fluorine atoms, an insulating layer coating solution containing the organic thin film transistor insulating layer material and a solution containing no fluorine is applied to a bank having a lyophilic portion and a liquid repellent portion. When the organic thin film transistor insulating layer is formed, the movement of the insulating layer coating liquid to the liquid repellent portion of the bank can be suppressed.

When forming an organic semiconductor layer by applying an organic semiconductor coating liquid containing an organic semiconductor compound and a fluorine-free solvent on the organic thin film transistor insulating layer, the film and the organic thin film transistor insulating layer have excellent affinity. A uniform organic semiconductor layer can be formed.

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. Groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms, including straight-chain hydrocarbon groups having 1 to 6 carbon atoms, branched hydrocarbon groups having 3 to 6 carbon atoms, and 3 to 6 carbon atoms. A cyclic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms are preferred.
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.

Specific examples of the monovalent organic group having 1 to 20 carbon atoms which may be substituted with a fluorine atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, tert-Butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentynyl, cyclohexynyl, trifluoromethyl, trifluoroethyl, phenyl, naphthyl, anthryl, tolyl, xylyl Group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, propylphenyl group, butylphenyl group, methylnaphthyl group, dimethylnaphthyl group, trimethylnaphthyl group, vinylnaphthyl group, ethenylnaphthyl group, methyl Anthryl group, Chiruansuriru group, chlorophenyl group, and, bromo phenyl group.
As the monovalent organic group having 1 to 20 carbon atoms, an alkyl group is preferable.

In the formula (1), R _aa represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. The connecting portion may be a divalent group having a structure that does not exhibit reactivity under environmental conditions for crosslinking the organic thin film transistor insulating layer material of the present invention. Examples of the linking moiety include a bond composed of a divalent organic group having 1 to 20 carbon atoms, an ether bond (—O—), a ketone bond (—CO—), and an ester bond (—COO—, —OCO—). Amide bond (—NHCO—, —CONH—), urethane bond (—NHCOO—, —OCONH—) and a combination of these bonds. a represents an integer of 0 or 1. In one certain form, a is 0.

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. 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. And a divalent cyclic hydrocarbon group having 3 to 20 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like. 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 an alkyl group or the like is preferable.

Examples of the divalent aliphatic hydrocarbon group and the divalent cyclic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, a dimethylpropylene group, Examples include 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 be substituted with an alkyl group include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.

In formula (1), R ₂ and R ₃ each independently represent a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. Definitions and specific examples of monovalent organic groups having 1 to 20 carbon atoms represented by R ₂ and R ₃ are the definitions and specific examples of monovalent organic groups having 1 to 20 carbon atoms represented by R described above. Is the same. In one certain form, R < ₂ > and R < ₃ > is an ethyl group.

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

The polymer compound (A) of the present invention may have a side chain group having a double bond.
This is because the number of reaction sites of the dithiocarbamylmethylphenyl group increases and the crosslink density of the cured film increases.

In that case, the polymer compound (A) is a high polymer containing at least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (3) and the repeating unit represented by the above formula (4). The molecular compound (A-1) is preferable.

In formula (3), R ₆ represents a hydrogen atom or a methyl group. In some one aspect, R ₆ is a methyl group.

In formula (3), R _bb represents a linking moiety that links the main chain and the side chain of the polymer compound and may have a fluorine atom. The definition and specific examples of the linking moiety represented by R _bb are the same as the definition and specific examples of the linking moiety represented by R _aa described above. In one certain form, R _bb is a bond represented by —COO—CH ₂ CH ₂ —.
b represents an integer of 0 or 1. In one certain form, b is 1.

In formula (4), R ₇ represents a hydrogen atom or a methyl group. In some one aspect, R ₇ is a methyl group.

In the formula (4), R _cc represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. The definition and specific examples of the connecting part represented by R _cc are the same as the definition and specific examples of the connecting part represented by R _aa described above. In one embodiment, R _cc is a bond represented by —COO—CH ₂ CH ₂ —NH—CO—NH—.
c represents an integer of 0 or 1. In one certain form, c is 1.

In the formula (4), m represents an integer of 1 to 5. In one certain form, m is 1.

In the formula (4), R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ′ are the same as the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. is there. In one certain form, R 'is a hydrogen atom.

The polymer compound (A) used in the present invention is obtained by, for example, a method in which a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is polymerized using a photopolymerization initiator or a thermal polymerization initiator. Can be manufactured.

Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) include N, N-diethyldithiocarbamylmethylstyrene.

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, -Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl, benzyl dimethyl Examples include carbonyl compounds such as luketal, benzyl diethyl ketal and diacetyl, sulfur compounds such as anthraquinone derivatives such as methyl anthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, thioxanthone derivatives, diphenyl disulfide and dithiocarbamate. .

When light energy is used as the energy for initiating polymerization, the wavelength of light irradiated to the polymerizable monomer is 360 nm or 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 paro Diacyl peroxides such as sid, o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide Hydroperoxides such as oxide and tert-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, and tris (tert-butylperoxy) triazine 1,1-di-tert-butylperoxycyclohexane, peroxyketals such as 2,2-di (tert-butylperoxy) butane, tert-butylperoxypivalate, tert-butylperoxy -2-Ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, tert-butylperoxy-3,5,5- Alkyl peresters such as trimethylhexanoate, tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate And peroxycarbonates such as tert-butylperoxyisopropyl carbonate.

Also, in a preferred embodiment, the polymer compound (A) has the formula

[Wherein, R, R ₁ , R _aa , a and n are as defined above, and X is a halogen atom. ]
Can be produced by a method in which a polymerizable monomer having a structure represented by the following formula is polymerized using a photopolymerization initiator or a thermal polymerization initiator and then reacted with a metal salt of N, N-dialkylthiocarbamic acid.

The polymer compound (A) having a side chain group having a double bond (for example, the polymer compound (A-1)) includes, for example, a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) Produced by a method in which a polymerizable monomer having active hydrogen is copolymerized using a photopolymerization initiator or a thermal polymerization initiator and then reacted with a compound containing a functional group that reacts with active hydrogen and a terminal double bond. I can do it. 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.

Examples of the polymerizable monomer having active hydrogen include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyphenyl acrylate, Acrylic acid-2-hydroxyphenylethyl 2-aminoethyl methacrylate, methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-3-hydroxypropyl, methacrylic acid-2-hydroxybutyl 4-hydroxyphenyl methacrylate, 2-hydroxyphenyl ethyl methacrylate, 4-aminostyrene, 4-allylaniline, 4-aminophenyl vinyl ether, 4- (N-phenylamino) phenyl allyl ether, 4- (N Methylamino) phenyl allyl ether, 4-aminophenyl allyl ether, allylamine, 2-aminoethyl acrylate, 4-hydroxystyrene, and include 4-hydroxy-allyl benzene. Examples of the compound containing a functional group that reacts with active hydrogen and a terminal double bond include acryloyl chloride, methacryloyl chloride, acrylic anhydride, methacrylic anhydride, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, Examples include 4-vinylbenzoyl chloride and 4-vinylphenyl isocyanate.

The polymer compound (A) and the polymer compound (A-1) polymerize a polymerizable monomer other than a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) and a polymerizable monomer having active hydrogen. Sometimes it may be added and manufactured.

Additional polymerizable monomers used include, for example, monomers having a double bond and an isocyanato group blocked with a blocking agent or an isothiocyanate group blocked with a blocking agent, acrylates and derivatives thereof, Acrylic esters and derivatives thereof, styrene and derivatives thereof, vinyl acetate and derivatives thereof, methacrylonitrile and derivatives thereof, acrylonitrile and derivatives thereof, vinyl esters of organic carboxylic acids and derivatives thereof, allyl esters of organic carboxylic acids and derivatives thereof, fumar Dialkyl esters of acids and derivatives thereof, dialkyl esters of maleic acid and derivatives thereof, dialkyl esters of itaconic acid and derivatives thereof, N-vinylamide derivatives of organic carboxylic acids, terminal unsaturated hydrocarbons and derivatives thereof, and , Organogermanium derivatives containing an unsaturated hydrocarbon group.

The type of polymerizable monomer used additionally is appropriately selected according to the 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 compounds (A) and (A) such as methacrylic acid ester and derivatives thereof, acrylic acid ester and derivatives thereof, and the like. A monomer that imparts plasticity to -1) is selected.

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

The acrylic acid esters and derivatives thereof may be monofunctional acrylates or polyfunctional acrylates 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, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol di Acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol Rupentaacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- ( Perfluoro-7-methyloctyl) ethyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9 Hexadecafluorononyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, N, N-dimethylacrylamide, N, N-diethylacrylamide, and N- An acryloyl morpholine is mentioned.

The methacrylic acid esters and derivatives thereof may be monofunctional methacrylates, and may be polyfunctional methacrylates although there are restrictions on the amount used. Examples of methacrylic acid esters and derivatives thereof include, for example, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, -Sec-butyl acrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, Ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethyl Propane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol pentamethacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (Perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3- Methylbutyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 1H, 1H, 3H-tetrafluoropropylme Acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate, 1H-1- (trifluoromethyl) trifluoro Examples thereof include ethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, and N-acryloylmorpholine.

Examples of styrene and its derivatives 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, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinyl Phenyl, 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, o-trifluoromethylstyrene, m-trifluoromethylstyrene, p-trifluoromethylstyrene, o-2,2,2-trifluoroethylstyrene, m-2,2, 2-trifluoroethylstyrene, p-2,2,2-tri Fluoroethylstyrene, o-2,2,3,3,3-pentafluoropropylstyrene, m-2,2,3,3,3-pentafluoropropylstyrene, p-2,2,3,3,3 -Pentafluoropropylstyrene and pentafluorostyrene.

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 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.

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.

As the polymerizable monomer used additionally, acrylic acid alkyl ester, methacrylic acid alkyl ester, styrene, acrylonitrile, methacrylonitrile and allyltrimethylgermanium are preferable.

The charged molar ratio of the monomer serving as the raw material of the repeating unit represented by the formula (1) is preferably 0.1 mol% or more and 50 mol% or less, more preferably 1 mol among all the monomers involved in the polymerization. % Or more and 30 mol% or less. By adjusting the charged molar ratio of the monomer within this range, a crosslinked structure is sufficiently formed inside the insulating layer.

The weight average molecular weight in terms of polystyrene of the polymer compound (A) and the polymer compound (A-1) is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 500,000. The polymer compound (A) and the polymer compound (A-1) may be linear, branched or cyclic.

Examples of the polymer compound (A) include poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl- Methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5'- Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino) Carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5 '-Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium) and poly (N, N-diethyldithiocarbamylmethylstyrene-co-styrene-co-4-methoxystyrene-co- [2 -[O- (1'-methylpropylideneamino) carboxyamino] Ethyl-methacrylate]).

Examples of the polymer compound (A-1) include poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [O- (1 ′ -Methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co- [2- [1'- (3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co -[2- [O- (1'-methylpropylideneamino) carboxy Mino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co- [2- [1 '-(3' , 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-acrylonitrile-co- [2 -[O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate) Co-styrene-co-acrylo Tolyl-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co -2-methacryloyloxyethyl methacrylate-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N -Diethyldithiocarbamylmethylstyrene-co-2-methacryloyloxyethyl methacrylate-co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl- Methacrylate] -co- [2- [1 '-(3', 5'-dimethylpyrazolyl) carbo Ruamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co- [2- [O -(1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate]- Co-styrene-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-Vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylic Nitrile-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinyl Phenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [1 ′-(3 ′, 5′-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]), poly (N, N -Diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [O- (1'-methylpropylideneamino ) Carboxyamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate] -co-styrene-co-acrylonitrile-co- [2- [1 '-(3', 5 ' -Dimethylpyrazolyl) carbonylamino] ethyl-methacrylate] -co-allyltrimethylgermanium), poly (N, N-diethyldithiocarbamylmethylstyrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl methacrylate]- Co-styrene-co-4-methoxystyrene-co- [2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl-methacrylate]) and poly (N, N-diethyldithiocarbamylmethyl) Styrene-co- [2- (4-vinylphenylaminocarbonylamino) ethyl Tacrylate] -co-styrene-co-4-methoxystyrene-co- [2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl-methacrylate] -co- [2- [1 '-(3 ', 5'-dimethylpyrazolyl) carbonylamino] ethyl-methacrylate]).

<Double bond compound (B)>
The double bond compound (B) is preferably a compound having a terminal double bond, and more preferably a compound having two or more terminal double bonds. A terminal double bond means the double bond located in the terminal of the chain | strand-shaped part of a compound. In this case, the chain portion may be a main chain or a branched chain of the compound. The double bond compound (B) may be a low molecular compound or a high molecular compound.

For example, the double bond compound (B) includes a divalent organic group represented by the above formula (2), that is, a divalent organic group having a structure in which a disubstituted carbylene group is bonded to an oxycarbonyloxylene group and It is a low molecular double bond compound (B-1) containing at least one double bond.

The organic group represented by the above formula (2) is decomposed when an acid is acted thereon. Therefore, when used with a photoacid generator, the organic thin film transistor insulating layer material of the present invention can exhibit a positive photosensitive function.

In formula (2), R ₄ and R ₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₄ and R ₅ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. Is the same. In some one aspect, _{R 4} and _{R 5} are methyl groups.

A preferred example of the double bond compound (B-1) is a low molecular double bond compound represented by the above formula (5).

In the formula (5), R ₈ to R ₁₂ and R ₁₇ to R ₂₁ represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₈ to R ₁₂ and R ₁₇ to R ₂₁ are the monovalent organic groups having 1 to 20 carbon atoms represented by R described above. The definition and specific examples of the group are the same. In one certain form, R ₈ to R ₁₂ and R ₁₇ to R ₂₁ are hydrogen atoms.

In the formula (5), R ₁₃ to R ₁₆ represent a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. The definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ₁₃ to R ₁₆ are the definition and specific examples of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. Is the same. In one certain form, R ₁₃ to R ₁₆ are methyl groups.

In formula (5), R _dd , R _ee and R _ff each independently represent a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom.

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. 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. And a divalent cyclic hydrocarbon group having 3 to 20 carbon atoms and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted with an alkyl group or the like. 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 an alkyl group or the like is preferable.

Examples of the divalent aliphatic hydrocarbon group and the divalent cyclic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an isopropylene group, an isobutylene group, a dimethylpropylene group, Examples include 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 be substituted with an alkyl group include, for example, a phenylene group, a naphthylene group, an anthrylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylenephenylene group, Diethylenephenylene group, triethylenephenylene group, propylenephenylene group, butylenephenylene group, methylnaphthylene group, dimethylnaphthylene group, trimethylnaphthylene group, vinylnaphthylene group, ethenylnaphthylene group, methylanthrylene group, and An ethylanthrylene group may be mentioned.

In formula (5), p1, p2 and p3 each independently represent an integer of 0 or 1. In one embodiment, p1 is 1, p2 is 1, and p3 is 1.

The double bond compound (B-1) is prepared, for example, by reacting bromophenyl chloroformate with 2,5-dimethylhexane-2,5-diol in the presence of a deoxidizing agent, It can be produced by a method of coupling the reaction intermediate and vinylphenylboronic acid.

Examples of the double bond compound (B-1) include 2,3-bis (4′-vinylbiphenyl-4-oxycarbonyloxy) butane and 2,5-bis (4′-vinylbiphenyl-4-oxycarbonyl). Oxy) hexane.

In addition, for example, the double bond compound (B) includes at least one repeating unit selected from the group consisting of a repeating unit represented by the above formula (3) and a repeating unit represented by the above formula (4). This is a polymer double bond compound (B-2) to be contained. In this case, in formula (3), the definitions of R ₆ , R _bb and b are the same as described above. In the formula (4), the definitions of R ₇ , R _cc , R ′, c and m are the same as described above.

The polymer double bond compound (B-2) is obtained by, for example, polymerizing a polymerizable monomer having active hydrogen using a photopolymerization initiator or a thermal polymerization initiator, and then reacting with a functional group that reacts with active hydrogen and a terminal group. It can be produced by a method of reacting with a compound containing a heavy bond. In this case, the meaning of the polymerizable monomer having active hydrogen is the same as described above. The definition of the compound containing a functional group that reacts with active hydrogen and a terminal double bond is the same as described above.

The polymer double bond compound (B-2) may be produced by adding a polymerizable monomer other than the polymerizable monomer having active hydrogen during the polymerization.

The addition amount of the double bond compound (B) contained in the organic thin film transistor insulating layer material of the present invention is 0.1 to about 0.1 to the amount of the repeating unit having the first functional group in the polymer compound (A). 1.0 equivalent is preferable, and 0.3 to 5 equivalent is more preferable. When the addition amount of the double bond compound (B) is outside the above range, the formation of the crosslinked structure may be insufficient.

<Organic thin film transistor insulating layer material>
The organic thin film transistor insulating layer material of the present invention includes a solvent for mixing and viscosity adjustment, a crosslinking agent used for crosslinking the polymer compound (A) and the polymer compound (A-1), and a combination with the crosslinking agent. Additives used in the process may be included. Solvents used include ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, alicyclic hydrocarbon solvents such as cyclohexane, unsaturated hydrocarbon solvents such as pentene, and aromatic 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. Moreover, as an additive, the catalyst for promoting a crosslinking reaction, a sensitizer, a leveling agent, a viscosity modifier, etc. can be used.

Examples of the catalyst for promoting the crosslinking reaction include a photoacid generator, a thermal acid generator, and a photocationic polymerization initiator.

It is preferable to add a photoacid generator or a thermal acid generator to the organic thin film transistor insulating layer material of the present invention. Examples of the photoacid generator and thermal acid generator include diazomethane derivatives, triazine derivatives, iodonium salts, and sulfonium salts. Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane. Examples of triazine derivatives include 2-methyl-4,6-ditrichloromethyl-triazine. Examples of the iodonium salt include tolylcumyl iodonium tetrakis (pentafluorophenyl) borate. Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate.

Further, as the photoacid generator and the thermal acid generator, in addition to the above materials, compounds described in JP-A-9-118663 and compounds described in JP2007-262401A can be used.

Examples of the crosslinking agent include divinylbenzene, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate.

The organic thin film transistor 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 an overcoat layer or a gate insulating layer. The organic thin film transistor insulating layer material is preferably an organic thin film transistor overcoat layer composition or an organic thin film transistor gate insulating layer composition, and more preferably an organic thin film transistor gate insulating layer material.

<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. It can be manufactured by forming a drain electrode and forming an overcoat. 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. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat 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. 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. Moreover, it can also be used for forming an overcoat layer as an organic thin film transistor overcoat layer material.

For the formation of the gate insulating layer or overcoat layer, if necessary for the organic thin film transistor insulating layer material, a solvent or the like is added to prepare an insulating layer coating solution, and the insulating layer coating solution is placed under the gate insulating layer or overcoat layer. It is performed by applying to the surface of the layer located, drying and curing. The organic solvent used in the insulating layer coating solution is not particularly limited as long as it dissolves the organic thin film transistor insulating layer material, but is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. at normal pressure. . Examples of the organic solvent include 2-heptanone (boiling point 151 ° C.) and propylene glycol monomethyl ether acetate (boiling point 146 ° C.). A leveling agent, a surfactant, a curing catalyst, and the like can be added to the insulating layer coating solution as necessary. The organic thin film transistor insulating layer material of the present invention can also be used for forming a gate insulating layer as an organic thin film transistor gate insulating layer composition.

The insulating layer coating solution can be applied onto the gate electrode by a known method such as spin coating, die coating, screen printing, or ink jet. The formed coating layer is dried as necessary. Drying here means removing the solvent contained in the applied resin composition.

The dried coating layer is then cured. Curing means that the organic thin film transistor insulating layer material is crosslinked. Cross-linking of the transistor insulating layer material is performed, for example, by applying electromagnetic wave irradiation or heat to the coating layer.

When the organic thin film transistor insulating layer material of the present invention is irradiated with electromagnetic wave or electron beam or applied with heat, the N, N-dialkyldithiocarbamyl group is eliminated and the generated radical reacts with the double bond in the double bond compound. A crosslinked structure is formed.

For example, the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; and irradiating the coating layer with an electromagnetic wave or an electron beam. It can form with the formation method including a process.

Also, for example, the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; and a step of applying heat to the coating layer Can be formed by a forming method including:

Further, for example, the organic thin film transistor insulating layer of the present invention is a step of applying a liquid containing an organic thin film transistor insulating layer material to a base material to form a coating layer on the base material; irradiating the coating layer with an electromagnetic wave or an electron beam And a step of applying heat to the coating layer.

When heat is applied to the coating layer, the coating layer is heated to a temperature of about 80 to 250 ° C., preferably about 100 to 230 ° C., and maintained for about 5 to 120 minutes, preferably about 10 to 60 minutes. If the heating temperature is too low or the heating time is too short, the insulating layer is not sufficiently crosslinked, and if the heating temperature is too high or the heating time is too long, the insulating layer may be damaged.

When irradiating the coating layer with electromagnetic waves, the irradiation conditions are adjusted in consideration of the degree of crosslinking and damage of the insulating layer. In the case of heating by applying a microwave, the application condition is adjusted in consideration of the cross-linking of the insulating layer and the degree of damage.

The wavelength of the electromagnetic wave to be irradiated 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 organic thin film transistor insulating layer material may be insufficiently crosslinked. As electromagnetic waves, ultraviolet rays are preferable.

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

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

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, gate electrode 2, source electrode 5, drain electrode 6 and organic semiconductor layer 4 may be composed of commonly used materials and methods. Resin or plastic plates, films, glass plates, silicon plates, etc. are used as the material of the substrate. 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.

The organic semiconductor layer can be formed, for example, by adding a solvent or the like if necessary for the organic semiconductor compound, preparing an organic semiconductor coating solution, applying the organic semiconductor coating solution on the gate insulating layer, and applying the organic semiconductor coating solution to the organic semiconductor coating solution. This is done by drying. 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 coating, screen printing, and ink jet, in the same manner as the insulating layer coating liquid.

The organic thin film transistor of the present invention may be coated with an overcoat material for the purpose of protecting the organic thin film transistor and improving the smoothness of the surface.

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

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

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

Hereinafter, although an example explains the present invention, the present invention is not limited to an example.

<Synthesis Example 1>
(Synthesis of polymer compound 1)
In a 50 ml pressure vessel (Ace), 2.36 g of 4- (1-ethoxyethoxy) styrene (Tosoh Organic Synthesis), 2.75 g of 4-vinylanisole (Aldrich), acrylonitrile (Wako Pure Chemical Industries) 0.87 g, 1.71 g of styrene (manufactured by Wako Pure Chemical Industries), 2.50 g of vinylbenzyl chloride (manufactured by Aldrich), 0 of 2,2′-azobis (2-methylpropionitrile) (manufactured by Wako Pure Chemical Industries) 0.05 g and 23.88 g of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and argon gas was bubbled and sealed.

Polymerization was performed in an oil bath at 60 ° C. for 20 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.

Polymer compound 1

<Synthesis Example 2>
(Polymer Compound 2)
6. In a 200 ml three-necked flask equipped with a Dimroth, 33.57 g of a propylene glycol monomethyl ether acetate solution of polymer compound 1 and sodium N, N-diethyldithiocarbamate trihydrate (manufactured by Wako Pure Chemical Industries) were added. 29 g, 0.1 g of methyltrioctylammonium chloride (manufactured by Aldrich, trade name “Aliquat 336” (registered trademark)) and 100 ml of propylene glycol monomethyl ether acetate were allowed to react at room temperature with stirring for 2 days. After completion of the reaction, the produced salt was filtered off, and the filtrate was concentrated with a rotary evaporator and reprecipitated with methanol to obtain a white solid. The obtained white solid was dissolved in 50 ml of acetone and reprecipitated with ion-exchanged water / methanol (1/2 (volume ratio)) to obtain polymer compound 2 as a white powder. The yield of the high molecular compound 2 was 7.60g. 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 obtained from the standard polystyrene of the polymer compound 2 was 134,000 (GPC manufactured by Shimadzu, one Tskel super HM-H + one Tskel super H2000, mobile phase = THF).

<Synthesis Example 3>
(Synthesis of polymer compound 3)
1.88 g of 2,1,3-benzothiadiazole-4,7-di (ethylene boronate) and 2,6-dibromo- (4,4-bis-hexadecanyl-4H-cyclopenta [2,1-b; In toluene (80 mL) containing 3.81 g of 3,4-b ′]-dithiophene), under nitrogen, 0.75 g of tetrakis (triphenylphosphine) palladium, methyltrioctylammonium chloride (manufactured by Aldrich, trade name “ 1.0 g of Aliquat 336 "(registered trademark)) and 24 mL of 2M aqueous sodium carbonate solution were added.

The mixture was vigorously stirred and heated to reflux for 24 hours. The viscous reaction mixture was poured into 500 mL of acetone to precipitate a fibrous yellow polymer. The polymer was collected by filtration, washed with acetone and dried in a vacuum oven at 60 ° C. overnight. The resulting polymer is referred to as polymer compound 3. The high molecular compound 3 has the following repeating unit. n indicates the number of repeating units.

Polymer compound 3

<Synthesis Example 4>
(Synthesis of double bond compound 1)
In a 150 ml three-necked flask equipped with a septum and a three-way cock, 5.00 g of 4-bromo-phenylchloroformate, 4.29 g of triethylamine and 100 ml of dehydrated tetrahydrofuran were placed and cooled in an ice bath. 1.55-g of 2,5-dimethyl-2,5-hexanediol was slowly added dropwise from a gas tight syringe. After completion of the dropwise addition, the mixture was reacted by stirring for 1 hour in an ice bath, and further stirred overnight at room temperature. After completion of the reaction, the reaction mixture was poured into water, the product was extracted with diethyl ether, the organic layer was further washed with water, then separated, and the organic layer was dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was filtered off, the filtrate was concentrated by a rotary evaporator to obtain 2,5-bis (4-bromophenyloxycarbonyloxy) -2,5-dimethylhexane as a viscous liquid. The yield of 2,5-bis (4-bromophenyloxycarbonyloxy) -2,5-dimethylhexane was 5.12 g.

2,5-bis (4-bromophenyloxycarbonyloxy) -2,5-dimethylhexane

To a 300 ml three-necked flask equipped with a Dimroth equipped with a three-way cock, 5.00 g of the obtained 2,5-bis (4-bromophenyloxycarbonyloxy) -2,5-dimethylhexane, 4-vinylphenyl 2.80 g of boronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.35 g of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), 200 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 20 ml of ion-exchanged water, and a stir bar were added. While stirring with a tic stirrer, argon was bubbled into the reaction mixture to create an argon atmosphere inside the flask. Add 0.084 g of tris (dibenzylideneacetone) dipalladium (0) (manufactured by Aldrich) and 0.107 g of tri-tert-butylphosphonium tetrafluoroborate, and immerse the flask in a 50 ° C. oil bath while continuing argon bubbling. For 7 hours. After completion of the reaction, the reaction solution was returned to room temperature, and the reaction mixture was transferred to a 500 ml separatory funnel. The flask was washed with 100 ml of toluene, and the washing solution was transferred to a separatory funnel. After the aqueous layer was separated, 50 ml of ion exchange water was added to wash the organic layer with water, and the aqueous layer was separated. After repeating the water washing step three times, the organic layer was separated and dried over anhydrous magnesium sulfate. After completion of drying, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated on a rotary evaporator. To the viscous liquid obtained, 100 ml of hexane was added to precipitate a solid, and the solid was filtered off with a glass filter and dried under reduced pressure to give 2,5-bis (4 ′-(4-vinylbiphenyl) oxy. Carbonyloxy) -2,5-dimethylhexane (double bond compound 1) was obtained as a single yellow solid. The yield of double bond compound 1 was 2.31 g.

Double bond compound 1

<Synthesis Example 5>
(Synthesis of polymer compound 4)
In a 50 ml pressure vessel (Ace), 1.50 g of 4- (1-ethoxyethoxy) styrene (Tosoh Organic Synthesis), 4.19 g of 4-vinylanisole (Aldrich), and styrene (Wako Pure Chemical Industries) 3.25 g, 1.11 g of 4-bromostyrene (manufactured by Aldrich), 0.05 g of 2,2′-azobis (2-methylpropionitrile) (manufactured by Wako Pure Chemical Industries), toluene (manufactured by Wako Pure Chemical Industries) 15.16 g was put, and argon gas was bubbled and sealed. Polymerization was carried out in an oil bath at 55 ° C. for 20 hours to obtain a viscous toluene solution.

In a 300 ml three-necked flask equipped with a Dimroth equipped with a three-way cock, 24.92 g of the resulting viscous toluene solution, 2.29 g of 4-vinylphenylboronic acid (manufactured by Tokyo Chemical Industry), potassium carbonate ( 5.35 g of Wako Pure Chemical Industries, Ltd.), 50 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 10 ml of ion-exchanged water, and a stir bar were added, and argon was bubbled into the reaction mixture while stirring with a magnetic stirrer. The inside of the flask was placed in an argon atmosphere. Into the flask, 0.071 g of tris (dibenzylideneacetone) dipalladium (0) (manufactured by Aldrich) and 0.09 g of tri-tert-butylphosphonium tetrafluoroborate were added, and the flask was kept at 50 ° C. while continuing argon bubbling. Immerse in an oil bath and let it react for 17 hours.

After completion of the reaction, the reaction solution was returned to room temperature, and the reaction mixture was transferred to a 500 ml separatory funnel.

The flask was washed with 100 ml of toluene, and the washing solution was transferred to a separatory funnel. After the aqueous layer was separated, 50 ml of ion exchange water was added to wash the organic layer with water, and the aqueous layer was separated. After repeating the water washing step three times, the organic layer was separated and dried over anhydrous magnesium sulfate. After drying, anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated with a rotary evaporator and reprecipitated with methanol. The precipitate was filtered and dried to obtain polymer compound 4 as a gray powder. The yield of the high molecular compound 4 was 1.83g. The high molecular compound 4 has the following repeating unit. The numbers in parentheses indicate the mole fraction of repeating units.

Polymer compound 4

The weight average molecular weight determined from the standard polystyrene of the polymer compound 4 was 500,000 (GPC manufactured by Shimadzu, one Tskel super HM-H + one Tskel super H2000, mobile phase = THF).

<Example 1>
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
In a 10 ml sample bottle, 0.4 g of the polymer compound 2 obtained in Synthesis Example 2, 0.04 g of the double bond compound 1 obtained in Synthesis Example 4 and 3.60 g of propylene glycol monomethyl ether acetate are stirred and stirred. Then, a uniform coating solution 1 as an organic thin film transistor insulating layer material was prepared.

The obtained coating solution was filtered using a membrane filter having a pore size of 0.2 μm, and the filtrate was spin-coated on a glass substrate with a chromium electrode, and then dried at 100 ° C. for 1 minute on a hot plate. Then, it baked at 200 degreeC for 30 minutes on the hotplate in nitrogen, and obtained the gate insulating layer.

Next, the polymer compound 3 is dissolved in xylene as a solvent to prepare a solution (organic semiconductor composition) having a concentration of 0.5% by weight, and the solution is filtered through a membrane filter to prepare a coating solution. did.

The obtained coating solution is applied on the gate insulating layer by a spin coating method to form an active layer having a thickness of about 30 nm, and then, on the active layer by a vacuum deposition method using a metal mask, A field effect organic thin film transistor was manufactured by forming a source electrode and a drain electrode (having a laminated structure in the order of molybdenum oxide and gold from the active layer side) having a channel length of 20 μm and a channel width of 2 mm.

<Evaluation of transistor characteristics>
The field effect organic thin film transistor thus fabricated has the transistor characteristics of a vacuum probe (BCT22MDC-5-5) under the condition that the gate voltage Vg is changed to 20 to -40V and the source-drain voltage Vsd is changed to 0 to -40V. HT-SCU (manufactured by Nagase Electronic Equipments Service Co., LTD).

The hysteresis of the field effect organic thin film transistor is that the source-drain voltage Vsd is −40 V, and the threshold voltage Vth1 and the gate voltage Vg when the gate voltage Vg is changed from 20 V to −40 V are changed from −40 V to 20 V. It was expressed as a voltage difference from the threshold voltage Vth2. The results are shown in Table 1.

<Example 2>
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
In a 10 ml sample bottle, 0.4 g of the polymer compound 2 obtained in Synthesis Example 2, 0.04 g of the double bond compound 1 obtained in Synthesis Example 4, and 0.04 g of the polymer compound 4 obtained in Synthesis Example 5 were added. 04 g and 4.10 g of propylene glycol monomethyl ether acetate were added and dissolved while stirring to prepare a uniform coating solution 2 as an organic thin film transistor insulating layer material. A field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the coating solution 2 was used instead of the coating solution 1, and the transistor characteristics were measured. The results are shown in Table 1.

<Example 3>
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
In a 10 ml sample bottle, 0.2 g of the polymer compound 2 obtained in Synthesis Example 2, 0.04 g of the double bond compound 1 obtained in Synthesis Example 4, and a photoacid generator (trade name: CPI-210S, Sunapro Co., Ltd.) (0.012 g) and propylene glycol monomethyl ether acetate (1.8 g) were added and dissolved while stirring to prepare a uniform coating solution 3 as an organic thin film transistor insulating layer material. The obtained coating solution 3 was filtered using a membrane filter having a pore size of 0.2 μm, and the filtrate was spin-coated on a glass substrate with a chromium electrode, and then dried at 100 ° C. for 1 minute on a hot plate. Thereafter, UV light (wavelength 365 nm) was irradiated at 600 mJ / cm ² using an aligner (manufactured by Canon; PLA-521) and baked in nitrogen at 200 ° C. for 30 minutes to obtain a gate insulating layer. The thickness of the obtained gate insulating layer was 406 nm.

A field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the gate insulating layer was prepared, and the transistor characteristics were measured. The results are shown in Table 1.

<Example 4>
(Production of organic thin film transistor insulating layer material and field effect organic thin film transistor)
In a 10 ml sample bottle, 0.2 g of the polymer compound 2 obtained in Synthesis Example 2, 0.02 g of the double bond compound 1 obtained in Synthesis Example 4, and a photoacid generator (trade name: CPI-210S, Sunapro Co., Ltd.) (0.011 g) and propylene glycol monomethyl ether acetate (1.8 g) were added and dissolved while stirring to prepare a uniform coating solution 4 as an organic thin film transistor insulating layer material.

A field effect organic thin film transistor was prepared in the same manner as in Example 3 except that the coating solution 4 was used instead of the coating solution 3, and the transistor characteristics were measured. The results are shown in Table 1. The thickness of the obtained gate insulating layer was 421 nm.

<Comparative Example 1>
(Manufacture of field-effect organic thin-film transistors)
In a 10 ml sample bottle, 1.00 g of polyvinylphenol-co-polymethyl methacrylate (manufactured by Aldrich, Mn = 6700), N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine (Sumitomo Chemical) 0.163 g, thermal acid generator (manufactured by Midori Chemical Co., Ltd., trade name: TAZ-108) 0.113 g, and 2-heptanone 7.00 g. Prepared.

A field effect organic thin film transistor was prepared in the same manner as in Example 1 except that the coating solution 5 was used instead of the coating solution 1, and the transistor characteristics were measured. The results are shown in Table 1.

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

Claims (9)

1. Formula (1)
   

   

   (1)
   [Wherein, R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. a represents an integer of 0 or 1, and n represents an integer of 1 to 5. When there are a plurality of R ₂ , they may be the same or different. When there are a plurality of R ₃ , they may be the same or different. When there are a plurality of R, they may be the same or different. ]
   A polymer compound (A) containing a repeating unit represented by the formula (A), and a double bond compound (B) which is a double bond compound containing two or more double bonds and is different from the polymer compound (A) An organic thin film transistor insulating layer material comprising:
2. The double bond compound (B) is a low molecular double bond compound (B-1) containing two or more double bonds, and a polymer two containing two or more repeating units containing double bonds. The organic thin film transistor insulating layer material according to claim 1, which is at least one selected from the group consisting of a heavy bond compound (B-2).
3. The low molecular double bond compound (B-1) is represented by the formula (2)
   

   

   (2)
   [Wherein, R ₄ and R ₅ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. ]
   The organic thin-film transistor insulating layer material according to claim 2, which is a low-molecular double bond compound containing a divalent organic group represented by formula (2) and two or more double bonds.
4. The low molecular double bond compound (B-1) is represented by the formula (5)
   

   

   (5)
   [Wherein R ₈ to R ₁₂ and R ₁₇ to R ₂₁ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R ₁₃ to R ₁₆ each independently represents a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _dd , R _ee and R _ff each independently represents a divalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the divalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. p1, p2 and p3 each independently represents an integer of 0 or 1. ]
   The organic thin film transistor insulating layer material according to claim 3, which is a low molecular double bond compound represented by the formula:
5. The polymer double bond compound (B-2) is represented by the formula (3):
   

   

   (3)
   [Wherein R ₆ represents a hydrogen atom or a methyl group. R _bb represents a connecting part that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. b represents an integer of 0 or 1. ]
   A repeating unit represented by formula (4):
   

   

   (4)
   [Wherein, R ₇ represents a hydrogen atom or a methyl group. R ′ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The hydrogen atom in the monovalent organic group having 1 to 20 carbon atoms may be substituted with a fluorine atom. R _cc represents a connecting portion that connects the main chain and the side chain of the polymer compound and may have a fluorine atom. c represents an integer of 0 or 1. m represents an integer of 1 to 5. When there are a plurality of R ′, they may be the same or different. ]
   The organic thin film transistor insulating layer material according to claim 2, which is a polymer double bond compound containing at least one type of repeating unit selected from the group consisting of repeating units represented by the formula:
6. An organic thin film transistor having an organic thin film transistor insulating layer formed using the organic thin film transistor insulating layer material according to any one of claims 1 to 5.
7. The organic thin film transistor according to claim 6, wherein the organic thin film transistor insulating layer is a gate insulating layer.
8. A display member comprising the organic thin film transistor according to claim 6 or 7.
9. A display comprising the display member according to claim 8.

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