JP5938192B2 - Organic element materials - Google Patents

Description

  The present invention relates to a material for forming an organic element, and more particularly to a material for forming an insulating layer of an organic element.

  Organic elements such as organic thin film transistors, organic electroluminescence elements, and organic photoelectric conversion elements have a functional layer made of an organic material. A functional layer made of an organic material can be formed by application of a solution containing an organic material or film formation using a printing method, and can generally be formed more easily and at a lower temperature than a functional layer made of an inorganic material.

  Therefore, an organic element may be able to manufacture a large number of elements at a low cost on a large-area substrate. In addition, a plastic substrate or a film can be used as the substrate of the element, and by using such a substrate, there is a case where an element that is flexible, lightweight, and hardly broken can be obtained.

  Furthermore, since there are a wide variety of organic materials, organic materials having a wide range of characteristic variations can be manufactured by using materials with different molecular structures for examination.

  However, some organic materials deteriorate in function due to the action of energy such as heat even when they are not heated to a very high temperature. Therefore, in order to obtain a higher-performance organic element, it is desirable to manufacture the organic element by using an organic material that can be heated as little as possible at the time of manufacturing the organic element and using a manufacturing method that requires as little heating as possible.

  Specifically, in a field effect organic thin film transistor which is a kind of organic element, a voltage applied to a gate electrode acts on a semiconductor layer to control on / off of a drain current. Therefore, in order to prevent drain current from flowing to the gate electrode, 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 thin film transistor device structure in which the organic semiconductor compound is exposed, it is essential to form an overcoat layer covering the entire device structure to protect the organic semiconductor compound from contact with the outside air. 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 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 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.

  In addition, the material as used in this specification is a concept including amorphous materials such as a polymer compound, a composition containing the polymer compound, a resin, and a resin composition. Moreover, the insulating layer as used in this specification is not limited to a layered member, and may broadly mean an insulating member in an organic element.

  The organic thin film transistor insulating layer material is required to have excellent insulating properties and excellent breakdown strength when formed into a thin film. In particular, in a bottom-gate field effect transistor, a 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 the organic semiconductor for forming an interface closely adhered to the organic semiconductor, and the organic semiconductor layer side surface of the film formed from the organic thin film transistor gate insulating layer material is flat. It is required to be.

  For example, Non-Patent Document 1 reports a gate insulating layer obtained by crosslinking poly (4-vinylphenyl-co-methyl methacrylate) (PVP-PMMA) at 150 ° C. as a gate insulating layer in an organic field effect transistor. Yes. However, the organic field effect transistor using the above resin for the insulating layer uses a high temperature process for manufacturing the insulating layer, and there is a problem that the absolute value of the threshold voltage (Vth) is not sufficiently small.

  Therefore, a material having a small absolute value of the threshold voltage (Vth) when used for an organic field effect transistor and capable of forming an organic layer by crosslinking the material at low temperature is desired. .

Appl. Phys. Lett. 92, 183306 (2008)

  The present invention solves the above-described conventional problems, and an object of the present invention is to provide an organic element material that can be crosslinked without performing a heat treatment at a high temperature.

  As a result of various studies in view of the above problems, the inventors have found that the above problems can be solved by using a specific organic element material, and have reached the present invention.

  That is, the present invention is an organic element material containing a polymer compound, the polymer compound comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), And the organic element material which is a high molecular compound which has at least 1 sort (s) of repeating unit chosen from the group which consists of a repeating unit represented by following formula (3).

（１）

(1)

[Wherein, R ₁ represents a hydrogen atom or a methyl group. 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. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. a represents an integer of 0 or 1, and b represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of Rf, they may be the same or different. ]
A repeating unit represented by:

（２）

(2)

[Wherein R ₂ represents a hydrogen atom or a methyl group. R _{3 to} R ₉ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. R _bb represents a linking moiety that links the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. ]

A repeating unit represented by:

（３）

(3)

[Wherein, R ₁₀ represents a hydrogen atom or a methyl group. R _{11 to} R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group 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. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. ]

Repeating unit represented by

  In one certain aspect, the said organic element material is an organic thin-film transistor insulating-layer material.

The present invention also includes a step of applying a liquid containing the organic element material onto a surface of a member constituting the organic element to form a coating layer; and irradiating the coating layer with light or an electron beam. Cross-linking organic element material, thereby forming an organic element insulating layer;
A method for forming an organic element insulating layer having the following is provided.

  In one certain aspect, the said light has a wavelength of 150-450 nm.

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

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

  Moreover, this invention provides the member for a display formed using the said organic element material.

  Moreover, this invention provides the display containing the said member for a display.

  The organic element material of the present invention can be crosslinked at a low temperature. In addition, when the organic element material of the present invention is used as a material for forming an organic thin film transistor insulating layer, the absolute value of the threshold voltage (Vth) of the organic thin film transistor is reduced.

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

Next, the present invention will be described in more detail.
In the present specification, the “polymer compound” refers to a compound containing a structure in which a plurality of the same structural units are repeated in the molecule, and includes a so-called dimer. On the other hand, the “low molecular compound” means a compound that does not have the same structural unit repeatedly in the molecule.

<Organic materials>
The organic material means a material made of an organic compound or a material containing an organic compound.
<Organic element>
An organic element means an element having a functional layer made of an organic material. Here, the “functional layer” means a layer having an electrical function.
<Organic element material>

An organic element material means the organic material used in order to form the functional layer which comprises organic elements, such as an organic thin-film transistor, an organic electroluminescent element, and an organic photoelectric conversion element.
Examples of the organic element material include an organic thin film transistor material used for an organic thin film transistor, an organic electroluminescence element material used for an organic electroluminescence element, and an organic photoelectric conversion element material used for an organic photoelectric conversion element. Examples of the organic thin film transistor material include organic thin film transistor insulating layer materials used for insulating layers such as a gate insulating layer and an overcoat layer.

  The organic element material of the present invention contains a fluorine compound and a polymer compound containing a group that can form a crosslinked structure without being treated at high temperature, or contains a fluorine atom and is crosslinked without being treated at high temperature. It is a composition containing a polymer compound containing a group capable of forming a structure.

  By introducing fluorine into the organic element material, the organic layer formed from the organic element material has low polarity, and polarization of the organic layer is suppressed. Moreover, when a crosslinked structure is formed inside the organic layer, the movement of molecules in the organic layer is suppressed, and the polarization of the organic layer is suppressed. In particular, when a gate insulating layer that is one embodiment of an organic layer is formed using an organic element material, polarization of the gate insulating layer is suppressed, hysteresis of the organic thin film transistor including the gate insulating layer is reduced, and operation accuracy is improved. improves.

  The fluorine atom preferably does not replace the hydrogen atom in the main chain of the polymer compound, but replaces the hydrogen atom in the side chain or side group (pendant group). When the fluorine atom is substituted with a side chain or a side group, the affinity of the polymer compound for other organic materials such as an organic semiconductor is not lowered, and in the formation of the layer containing the organic material, the organic material is It becomes easy to form a layer in contact with the exposed surface of the organic layer formed from the polymer compound.

  The group that can form a crosslinked structure may be any group that can react with other groups and dimerize. Groups that can be dimerized by reacting with each other can form a crosslinked structure inside the organic layer by bonding two groups.

  The group that can be dimerized by reacting with another group is a functional group that absorbs light energy or electron energy to cause a dimerization reaction (referred to as “photodimerization reactive group” in this specification). Is preferred. The reason why the photodimerization reactive group is preferable is that it is not necessary to perform heat treatment for a long time at a high temperature in order to crosslink the organic element material, and the deterioration of the organic element characteristics in the process of forming the organic layer is suppressed. In particular, when an organic element material is used for an insulating layer of an organic thin film transistor, deterioration in characteristics of the organic thin film transistor in the process of forming the insulating layer is suppressed.

  The light absorbed by the photodimerization reactive group has a high energy because the photodimerization reactive group remaining when the organic device material is formed by the photopolymerization method may react if the energy is too low. Are preferred. Preferable light that the photodimerization reactive group absorbs is ultraviolet light, for example, light having a wavelength of 450 nm or less, preferably 150 to 450 nm.

  Dimerization here means that two molecules of an organic compound are chemically bonded. The molecules to be bound may be the same or different. The chemical structures of the functional groups involved in dimerization in the two molecules to be dimerized may be the same or different. However, it is preferable that the functional group has a structure and a combination that cause a photodimerization reaction even when a reaction aid such as a catalyst and an initiator is not used. This is because contact with the residue of the reaction aid may cause deterioration of surrounding organic materials.

  Examples of preferable groups containing a fluorine atom include an aryl group in which a hydrogen atom is substituted with fluorine, an alkylaryl group in which a hydrogen atom is substituted with fluorine, particularly a phenyl group in which a hydrogen atom is substituted with fluorine, and a hydrogen atom in fluorine. A substituted alkylphenyl group;

  Preferred examples of the photodimerization reactive group include an aryl group in which a hydrogen atom is substituted with a halomethyl group, a vinyl group in which the hydrogen atom at the 2-position is substituted with an aryl group, and a hydrogen atom at the 2-position is substituted with an arylcarbonyl group A vinyl group, particularly preferably a phenyl group in which a hydrogen atom is substituted with a halomethyl group, a vinyl group in which the hydrogen atom at the 2-position is substituted with a phenyl group, and a vinyl in which the hydrogen atom at the 2-position is substituted with a phenylcarbonyl group It is a group. When the basic skeleton of the side group of the repeating unit is an aryl group or a phenyl group, the affinity for other organic materials such as an organic semiconductor is improved, and the layer containing the organic material is formed from the polymer compound. It becomes easy to form a flat layer in contact with the exposed surface of the organic layer.

  An aryl group in which a hydrogen atom is substituted with a halomethyl group and a phenyl group in which a hydrogen atom is substituted with a halomethyl group, when irradiated with ultraviolet light or an electron beam, the halogen is eliminated to generate a benzyl type carboradical. When the two generated carbo radicals are combined, a carbon-carbon bond is formed (radical coupling), and the organic thin film transistor insulating layer material is cross-linked. In the case of a vinyl group in which the hydrogen atom at the 2-position is substituted with an aryl group or a phenyl group, a vinyl group in which the hydrogen atom at the 2-position is substituted with an arylcarbonyl group or a phenylcarbonyl group, etc. When irradiated, a 2 + 2 cyclization reaction occurs and the organic thin film transistor insulating layer material is crosslinked.

  The polymer compound containing a fluorine atom preferably contains a repeating unit having a group containing a fluorine atom. The repeating unit having a group containing a fluorine atom is preferably a repeating unit represented by the above formula (1). The repeating unit having a photodimerization reactive group is preferably a repeating unit represented by the above formula (2) or a repeating unit represented by the above formula (3).

  That is, a preferred embodiment of the organic element material of the present invention is a group consisting of a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and a repeating unit represented by the formula (3). It is a high molecular compound which has at least 1 sort (s) of repeating unit chosen.

In formula (1), R ₁ represents a hydrogen atom or a methyl group. In one embodiment, R ₁ is a hydrogen atom.
R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound. The connecting portion may be a divalent group having a structure that does not exhibit reactivity under the environmental conditions for crosslinking the organic element material of the present invention. Specific examples of the linking moiety include a divalent organic group having 1 to 20 carbon atoms, a group consisting of an ether bond (—O—), a group consisting of a ketone bond (—CO—), an ester bond (—COO—, — A group consisting of OCO-), a group consisting of an amide bond (-NHCO-, -CONH-), a group consisting of a urethane bond (-NHCOO-, -OCONH-) and a group in which these groups are combined. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. a represents an integer of 0 or 1. In one embodiment, a is 0.
R represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. When there are a plurality of R, they may be the same or different. In one certain aspect, R is a hydrogen atom.
Rf represents a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom. When there are a plurality of Rf, they may be the same or different. In one certain aspect, Rf is a fluorine atom. b represents an integer of 1 to 5. In one embodiment, b is 5.

  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. For example, a divalent linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, 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.

  Specific 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, and a dimethylpropylene group. , Cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group and the like.

  Specific examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenylene group, naphthylene group, anthrylene group, dimethylphenylene group, trimethylphenylene group, ethylenephenylene group, diethylenephenylene group, triethylenephenylene group, Examples thereof include a propylene phenylene group, a butylene phenylene group, a methyl naphthylene group, a dimethyl naphthylene group, a trimethyl naphthylene group, a vinyl naphthylene group, an ethenyl naphthylene group, a methyl anthrylene group, and an ethyl anthrylene group.

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. And an aromatic hydrocarbon group having 6 to 20 carbon atoms.
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.

  When R is a monovalent organic group having 1 to 20 carbon atoms, the monovalent organic group having 1 to 20 carbon atoms does not have a fluorine atom. Specific examples of the monovalent organic group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, and cyclopropyl group. , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentynyl group, cyclohexylinyl group, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, Triethylphenyl, propylphenyl, butylphenyl, methylnaphthyl, dimethylnaphthyl, trimethylnaphthyl, vinylnaphthyl, ethenylnaphthyl, methylanthryl, ethylanthryl, chlorophenyl, bromophenyl, etc. It is done.

  Specific examples of the monovalent organic group having 1 to 20 carbon atoms having a fluorine atom represented by Rf include a pentafluorophenyl group and a trifluoromethylphenyl group.

In formula (2), R ₂ represents a hydrogen atom or a methyl group. In some aspect, R ₂ is hydrogen atom. R _{3 to} R ₉ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. In one certain aspect, R _{3 to} R ₉ are hydrogen atoms. R _bb represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. In one certain form, _Rbb is an ethylene group.

Even if the monovalent organic group having 1 to 20 carbon atoms represented by R _{3 to} R ₉ is a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom, the number of carbon atoms having no fluorine atom The monovalent organic group of 1-20 may be sufficient. The definition and specific example of the monovalent organic group having 1 to 20 carbon atoms which do not have a fluorine atom are the same as the definition and specific example of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. is there. Definition and specific example of a connecting part that connects the main chain and the side chain of the polymer compound represented by R _bb are the connections that connect the main chain and the side chain of the polymer compound represented by R _aa described above. The definition of the part is the same as the specific example.

In formula (3), R ₁₀ represents a hydrogen atom or a methyl group. In one embodiment, R ₁₀ is a hydrogen atom. R _{11 to} R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. In one embodiment, R _{11 to} R ₁₇ are hydrogen atoms. R _cc represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. In one certain form, _Rcc is a phenylene group.

Even if the monovalent organic group having 1 to 20 carbon atoms represented by R _{11 to} R ₁₇ is a monovalent organic group having 1 to 20 carbon atoms having a fluorine atom, the number of carbon atoms having no fluorine atom The monovalent organic group of 1-20 may be sufficient. The definition and specific example of the monovalent organic group having 1 to 20 carbon atoms which do not have a fluorine atom are the same as the definition and specific example of the monovalent organic group having 1 to 20 carbon atoms represented by R described above. is there.
Definition and specific example of a linking part that connects the main chain and the side chain of the polymer compound represented by R _cc are linking that connects the main chain and the side chain of the polymer compound represented by R _aa described above. The definition of the part is the same as the specific example.

  The polymer compound contained in the organic element material of the present invention includes a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (2). Is polymerized using a photopolymerization initiator or a thermal polymerization initiator, or a polymerizable monomer that is a raw material of a repeating unit represented by formula (1) and a raw material of a repeating unit represented by formula (3) Or a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) and a formula (2). It can be produced by a method in which a polymerizable monomer that is a raw material of the repeating unit and a polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) are polymerized using a photopolymerization initiator or a thermal polymerization initiator. . Among these, a method of polymerizing using a thermal polymerization initiator is preferable.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the above formula (1) include 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2,3,4,5,6-pentafluoro. Styrene, 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4-trifluoromethylstyrene, vinyl-4-trifluoromethylphenyl ether, vinyl-2-trifluoromethylbenzoate, vinyl-3-trifluoromethylbenzoate Vinyl-4-trifluoromethylbenzoate.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the above formula (2) include vinyl cinnamate, cinnamyl methacrylate, cinnamoyloxybutyl methacrylate, and cinnamyliminooxyiminoethyl methacrylate. The repeating unit represented by the formula (2) is a group obtained by removing two hydrogen atoms from a trans isomer compound, but a group obtained by removing two hydrogen atoms from a cis isomer compound is included in the organic element material of the present invention. The polymer compound may have. The polymerizable monomer that is a raw material of the repeating unit represented by the formula (2) may be a trans isomer or a cis isomer.

  Examples of the polymerizable monomer that is a raw material of the repeating unit represented by the above formula (3) include phenyl vinyl styryl ketone and phenyl (methacryloyloxystyryl) ketone. The repeating unit represented by the formula (3) is a group obtained by removing two hydrogen atoms from a trans isomer compound, but a group obtained by removing two hydrogen atoms from a cis compound is included in the organic element material of the present invention. The polymer compound may have. The polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) may be a trans isomer or a cis isomer.

  The organic element material of the present invention is a copolymer containing a repeating unit other than the repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3). It may be. The copolymer is represented by a polymerizable monomer that is a raw material of the repeating unit represented by the formula (1), a polymerizable monomer that is a raw material of the repeating unit represented by the formula (2), and a formula (3). It can be produced by adding a polymerizable monomer other than the polymerizable monomer as a raw material of the repeating unit during the polymerization.

  Examples of the polymerizable monomer used additionally include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl-2-methylbenzoate, vinyl-3-methylbenzoate, vinyl-4-methylbenzoate, Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl phenyl ether, vinyl benzyl ether, vinyl-4-methyl phenyl ether, styrene, α-methyl styrene, 2,4-dimethyl-α-methyl styrene, o -Methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2 , 4,6-trime Til styrene, 2,4,5-trimethyl styrene, pentamethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, o-bromo styrene, m-bromostyrene, p-bromostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, 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, diisopropyl Benzene, 4-aminostyrene, acrylonitrile, allyl acetate, allyl benzoate, N-methyl-N-vinylacetamide, 1-butene, 1-pentene, 1-hexene, 1-octene, vinylcyclohexane, vinyl chloride, allyltrimethylgermanium Allyltriethylgermanium, allyltributylgermanium, trimethylvinylgermanium, triethylvinylgermanium, methyl acrylate, ethyl acrylate, acrylate-n-propyl, isopropyl acrylate, acrylate-n-butyl Isobutyl acrylate, acrylate-sec-butyl, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isobornyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, N, N- Dimethylacrylamide, N, N-diethylacrylamide, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid sec-butyl, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate , Benzyl methacrylate, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, 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-perfluorohexyl-2-hydroxypropyl acrylate, 2 -(Perfluorooctyl) ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) ethyl acrylate, 3- ( -Fluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl acrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro- 5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl acrylate, 1H, 1H, 3H- Tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H, 1H, 9H-hexadecafluorononyl acrylate, 1H-1- (trifluorome ) Trifluoroethyl acrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (par Fluorobutyl) ethyl methacrylate, 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- (par -Fluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 3- ( Perfluoro-5-methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 9H-hexadecafluorononyl methacrylate Relate, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H- hexafluoro-butyl methacrylate and the like.

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

  When light energy is used as the energy for initiating copolymerization, 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 peroxy , Diacyl peroxides such as o-methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide , Hydroperoxides such as tert-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tris (tert-butylperoxy) triazine, Peroxyketals such as 1,1-di-tert-butylperoxycyclohexane and 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-trimethylhexa Alkyl peroxyesters such as noate, tert-butylperoxyacetate, tert-butylperoxybenzoate, di-tert-butylperoxytrimethyladipate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, Examples include peroxycarbonates such as tert-butylperoxyisopropyl carbonate.

  When heat energy is used as the energy for initiating copolymerization, the heating temperature of the polymerizable monomer is 40 to 150 ° C, preferably 50 to 80 ° C. The heating temperature of the polymerizable monomer may be appropriately adjusted depending on the type of thermal polymerization initiator used.

  The polymer compound contained in the organic element material of the present invention preferably has a weight average molecular weight of 3,000 to 1,000,000, and more preferably 5,000 to 500,000. The polymer compound may be linear, branched or cyclic.

  In the production of the polymer compound contained in the organic element material of the present invention, the amount of the polymerizable monomer used as the raw material of the repeating unit represented by the formula (1) is the amount of fluorine atoms introduced into the organic thin film transistor insulating layer material. The amount is adjusted to an appropriate amount.

  The amount of fluorine atoms introduced into the organic element material is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 5 to 40% by mass with respect to the mass of the organic element material. When the organic element material is used for an insulating layer of a field effect type organic thin film transistor, if the amount of fluorine atoms is less than 1% by mass, the effect of reducing the hysteresis of the organic field effect transistor may be insufficient. If it exceeds 60% by mass, the affinity for other organic materials may decrease, and it may be difficult to form a layer in contact with the exposed surface of the insulating layer.

  For example, in the production of the polymer compound, the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (1) is preferably 5 mol% or more with respect to the total of all monomers used for polymerization. It is 95 mol% or less, More preferably, it is 15 mol% or more and 85 mol% or less, More preferably, it is 30 mol% or more and 70 mol% or less.

  In the case where the polymer compound contained in the organic element material of the present invention contains a repeating unit represented by the formula (2), in the production of the polymer compound, polymerization that becomes a raw material of the repeating unit represented by the formula (2) The molar amount of the monomer to be charged is preferably 1 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 80 mol% or less, and still more preferably 10 mol%, based on the total of all monomers used for polymerization. The mol% is 70 mol% or more.

  When the organic element material is used for an insulating layer of a field effect type organic thin film transistor, when the charged amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (2) is less than 1 mol%, the organic thin film transistor is insulated. In some cases, the layer material cannot obtain sufficient solvent resistance, and when it is greater than 95 mol%, the storage stability of the organic thin film transistor insulating layer material may be poor.

  For example, in the production of the polymer compound, the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (2) is preferably 5 mol% or more with respect to the total of all monomers used for the polymerization. It is 95 mol% or less, More preferably, it is 15 mol% or more and 85 mol% or less, More preferably, it is 30 mol% or more and 70 mol% or less.

  When the polymer compound contained in the organic element material of the present invention contains a repeating unit represented by the formula (3), in the production of the polymer compound, polymerization that becomes a raw material of the repeating unit represented by the formula (3) The molar amount of the monomer to be charged is preferably 1 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 80 mol% or less, and still more preferably 10 mol%, based on the total of all monomers used for polymerization. The mol% is 70 mol% or more.

  When the organic element material is used for an insulating layer of a field effect type organic thin film transistor, when the charged amount of the polymerizable monomer serving as the raw material of the repeating unit represented by the formula (3) is less than 1 mol%, the organic thin film transistor is insulated. In some cases, the layer material cannot obtain sufficient solvent resistance, and when it is greater than 95 mol%, the storage stability of the organic thin film transistor insulating layer material may be poor.

  For example, in the production of the polymer compound, the charged molar amount of the polymerizable monomer that is a raw material of the repeating unit represented by the formula (3) is preferably 5 mol% or more with respect to the total of all monomers used for the polymerization. It is 95 mol% or less, More preferably, it is 15 mol% or more and 85 mol% or less, More preferably, it is 30 mol% or more and 70 mol% or less.

  Examples of the organic element material of the present invention include poly (styrene-co-vinylcinnamate-co-pentafluorostyrene), poly (styrene-co-vinylcinnamate-co-pentafluorostyrene-co-acrylonitrile), poly (Styrene-co-vinylcinnamate-co-pentafluorostyrene-co-acrylonitrile-co-allyltrimethylgermanium), poly (vinylcinnamate-co-pentafluorostyrene), poly (styrene-co-vinylcinnamate-co -4-chloromethylstyrene-co-pentafluorostyrene), poly (styrene-co-phenylvinylstyrylketone-co-pentafluorostyrene), poly (styrene-co-phenylvinylstyrylketone-co-pentafluorostyrene-co -Acrylonitrile), poly (Styrene-co-phenylvinylstyrylketone-co-pentafluorostyrene-co-acrylonitrile-co-allyltrimethylgermanium), poly (phenylvinylstyrylketone-co-pentafluorostyrene), poly (styrene-co-phenylvinylstyryl) Ketone-co-4-chloromethylstyrene-co-pentafluorostyrene), poly (styrene-co-phenyl (methacryloyloxystyryl) ketone-co-pentafluorostyrene), poly (styrene-co-phenyl (methacryloyloxy) Styryl) ketone-co-pentafluorostyrene-co-acrylonitrile), poly (styrene-co-phenyl (methacryloyloxystyryl) ketone-co-pentafluorostyrene-co-acrylonitrile-co-allyltrimethylgerma ), Poly (phenyl (methacryloyloxystyryl) ketone-co-pentafluorostyrene), poly (styrene-co-phenyl (methacryloyloxystyryl) ketone-co-4-chloromethylstyrene-co-pentafluorostyrene) Is mentioned.

<Organic thin film transistor insulating layer material>
The organic element material of the present invention can be used as an organic thin film transistor insulating layer material, thereby reducing the absolute value of the threshold voltage (Vth) of the organic thin film transistor. The organic thin film transistor insulating layer material of the present invention is at least one selected from the group consisting of a repeating unit represented by formula (1), a repeating unit represented by formula (2), and a repeating unit represented by formula (3). A polymer compound having a seed repeating unit is preferable.

  The organic element material of the present invention and the organic thin film transistor insulating layer material of the present invention may contain an organic solvent. The organic solvent is not particularly limited as long as it is a good solvent for the polymer compound and a poor solvent for the organic semiconductor compound. For example, butyl acetate, 2-heptanone, propylene glycol monomethyl Examples include ether acetate.

  The organic element material of the present invention and the organic thin film transistor insulating layer material of the present invention may contain a leveling agent or a surfactant.

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

  The bottom gate type organic thin film transistor is formed, for example, by forming a gate electrode on a substrate, forming a gate insulating layer on the gate electrode, forming an organic semiconductor layer on the gate insulating layer, and forming a source electrode and a drain on the organic semiconductor layer. It can be manufactured by forming an electrode and forming an overcoat layer. The organic thin film transistor insulating layer material of the present invention is suitably used for forming a gate insulating layer as an organic thin film transistor gate insulating layer material. 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 top-gate organic thin film transistor that is one embodiment of the present invention. The organic thin film transistor includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1, an organic semiconductor layer 4 formed on these electrodes with a channel portion interposed therebetween, and an organic semiconductor layer 4 A gate insulating layer 3 covering the entire element formed on the gate insulating layer 3 and a gate electrode 2 formed on the surface of the gate insulating layer 3 are provided.

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

  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. This is done by applying to the surface of the layer to be positioned, drying and curing. The organic solvent used in the insulating layer coating solution is not particularly limited as long as it dissolves a polymer compound, 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 and propylene glycol monomethyl ether acetate. A leveling agent, a surfactant, a curing catalyst, and the like can be added to the insulating layer coating solution as necessary.

  The insulating layer coating solution can be applied onto the gate electrode by a known spin coating, die coater, screen printing, ink jet or the like. The formed coating layer is dried as necessary. Drying here means removing the solvent of 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 realized, for example, by combining two photodimerization reactive groups. In that case, by irradiating the coating layer with light or electron beam, radical coupling reaction or cyclization reaction of the photodimerization reactive group of the polymer compound occurs, and the two photodimerization reactive groups are bonded. . Irradiation with light or an electron beam can be performed under a low temperature environment of 50 ° C. or less, preferably 5 to 40 ° C., for example, at room temperature (about 25 ° C.).

  In the case of irradiating ultraviolet rays among light, the irradiation of 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. it can. The electron beam irradiation can be performed using, for example, a micro electron beam irradiation tube.

  For example, when the photodimerization reactive group is a vinyl group in which the hydrogen atom at the 2-position is substituted with a phenyl group, or a vinyl group in which the hydrogen atom at the 2-position is substituted with a phenylcarbonyl group, the wavelength of the irradiated light is 150-450 nm, preferably 190-400 nm. When the wavelength of light to be irradiated is less than 150 nm, the molecular weight of the crosslinked polymer compound may be low, and when it exceeds 450 nm, the organic thin film transistor insulating layer material may be insufficiently crosslinked.

  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 in which an alkylchlorosilane compound or an alkylalkoxysilane compound is dissolved in an organic solvent in an amount of 1 to 10% by weight.

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

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

  The substrate 1, the gate electrode 2, the source electrode 5, the drain electrode 6 and the organic semiconductor layer 4 may be configured by materials and methods that are usually used. Resin and plastic plates, films, glass plates, silicon plates, and the like are used as the substrate material. As the 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 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. 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 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 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 preferably has a boiling point of 50 ° C. to 200 ° C. at normal pressure. Examples of the solvent include chloroform, toluene, anisole, 2-heptanone, and propylene glycol monomethyl ether acetate. The organic semiconductor coating liquid can be applied onto the gate insulating layer by a known method such as spin coating, die coater, screen printing, and ink jet as in the case of the insulating layer coating liquid.

  The 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.

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

<Organic electroluminescence device>
The organic element material of the present invention can also be used for an organic electroluminescence element. An organic electroluminescent element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent. As an example of an organic electroluminescence element, an element having an anode, a light emitting layer, and a cathode, and an anode having an electron transport layer containing an electron transport material between the cathode and the light emitting layer and adjacent to the light emitting layer, and light emission An element having a layer, an electron transport layer, and a cathode; and an anode, a hole transport layer, and a light emitting layer having a hole transport layer containing a hole transport material adjacent to the light emitting layer between the anode and the light emitting layer And an element having an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. The organic element material of the present invention is preferably used for producing an insulating member in the organic electroluminescence element.

<Organic photoelectric conversion element>
The organic element material of the present invention can also be used for an organic photoelectric conversion element. The organic photoelectric conversion element has an active layer between a pair of electrodes, at least one of which is transparent or translucent. The organic element material of the present invention is preferably used for producing an insulating member in the organic photoelectric conversion element.

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

Example 1
(Synthesis of polymer compound 1)
In a 100 ml three-necked flask equipped with a three-way cock, 20.07 g of 3-vinylbenzaldehyde (manufactured by Aldrich), 23.00 g of acetophenone (manufactured by Aldrich) and a stirrer were placed and stirred with a magnetic stirrer to prepare a uniform reaction mixture. Prepared. The flask was immersed in an ice bath, a catalytic amount of concentrated sulfuric acid was added to the reaction mixture while stirring, and the mixture was reacted for 1 hour under ice cooling.
The flask was removed from the ice bath, and the reaction mixture was continuously stirred at room temperature until the disappearance of the peak of vinylbenzaldehyde as a raw material was confirmed by NMR analysis. After completion of the reaction, the reaction mixture was transferred to a separatory funnel, 100 ml of diethyl ether was added, and washing with water was repeated until the aqueous layer became neutral. After completion of washing with water, the organic layer was separated, the organic layer was dried over magnesium sulfate, the organic layer was filtered, and the filtrate was concentrated with a rotary evaporator to obtain a crude 3-vinylstyrylphenyl ketone. The purity of 3-vinyl styryl phenyl ketone determined from NMR was 74%.

３−ビニルスチリルフェニルケトン

3-vinyl styryl phenyl ketone

  2,3,4,5,6-pentafluorostyrene (manufactured by Aldrich) 4.00 g, 3-vinyl styryl phenyl ketone 6.55 g, 2,2′-azobis (isobutyronitrile) 0.05 g, 2-heptanone 24.74 g (manufactured by Wako Pure Chemical Industries, Ltd.) was put into a 50 ml pressure vessel (made by Ace), bubbled with nitrogen, sealed, and polymerized in an oil bath at 60 ° C. for 48 hours. After completion of the reaction, the reaction mixture was dropped into 500 ml of 2-propanol to reprecipitate polymer compound 1, filtered and dried under reduced pressure to obtain polymer compound 1 as a pale yellow solid. The polymer compound 1 is used as an organic thin film transistor insulating layer material. The high molecular compound 1 has the following repeating unit. Here, the number in parentheses indicates the mole fraction of the repeating unit.

高分子化合物１

Polymer compound 1

  The weight average molecular weight calculated | required from the standard polystyrene of the obtained high molecular compound 1 was 56000. (Shimadzu GPC, 1 Tskel super HM-H + 1 Tskel super H2000, mobile phase = THF)

(Preparation of coating solution containing polymer compound 1 and organic solvent)
0.50 g of the polymer compound 1 and 2.00 g of 2-heptanone were placed in a 10 ml sample bottle and dissolved with stirring to prepare a uniform coating solution.

  The obtained coating solution was filtered using a membrane filter having a pore size of 0.2 μm to prepare a coating solution of polymer compound 1.

(Production of field-effect organic thin-film transistors)
A polystyrene-equivalent weight average molecular weight of 69,000, a copolymer consisting only of 9,9-dioctyl fluorenediyl group and bithiophenediyl group, and bithiophenediyl relative to 9,9-dioctyl fluorenediyl group A copolymer having a group molar ratio of 1 is dissolved in chloroform as a solvent to prepare a solution having a concentration of 0.5% by mass, and the solution is filtered through a membrane filter to prepare an organic semiconductor coating solution. did.

  The coating solution of polymer compound 1 was spin-coated on a glass substrate with a chromium electrode, and then dried by heating at 70 ° C. for 30 minutes on a hot plate. Thereafter, the polymer compound 1 was cross-linked by UV irradiation (wavelength: about 254 nm) for 1 minute at room temperature (25 ° C.) using a UV / ozone stripper (manufactured by Samco, UV-1) under a nitrogen atmosphere to obtain a thickness of about 580 nm. A gate insulating layer having a thickness was obtained. Since the high molecular compound 1 bridge | crosslinks at low temperature, the gate insulating layer was able to be formed at room temperature.

  Next, an organic semiconductor coating solution is applied on the gate insulating layer by a spin coating method to form an active layer having a thickness of about 60 nm, and then the active layer is formed on the active layer by a vacuum deposition method using a metal mask. Then, 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 were formed to produce a field effect organic thin film transistor.

<Transistor characteristics of field-effect organic thin-film transistors>
With respect to the field effect organic thin film transistor thus fabricated, the transistor characteristics were changed to a vacuum probe (BCT22MDC-5-5) under the condition that the gate voltage Vg was changed to 20 to -40V and the source-drain voltage Vsd was changed from 0 to -40V. HT-SCU; manufactured by Nagase Electronic Equipments Service Co. LTD). The results are shown in Table 1.

  The hysteresis of the organic thin film transistor is that when the source-drain voltage Vsd is -40V and the gate voltage Vg is changed from 0V to -40V, the threshold voltage Vth1 and the gate voltage Vg are changed from -40V to 0V. It was expressed as a voltage difference from the voltage Vth2.

Comparative Example 1
(Production of field-effect organic thin-film transistors)
1.00 g of polyvinylphenol-co-polymethyl methacrylate (manufactured by Aldrich, Mn = 6700), 0.163 g of N, N, N ′, N ′, N ″, N ″ -hexamethoxymethylmelamine (manufactured by Sumitomo Chemical), heat 0.113 g of acid generator (manufactured by Midori Chemical Co., Ltd., trade name: TAZ-108) and 7.00 g of 2-heptanone were placed in a 10 ml sample bottle and dissolved by stirring to prepare a uniform coating solution.

A field effect organic thin film transistor was prepared in the same manner as in Example 1 except that this coating solution was used for forming the gate insulating layer and baked at 200 ° C. for 30 minutes on a hot plate instead of UV irradiation, and the transistor characteristics were measured. ,evaluated.
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 layer.

Claims (8)

An organic element material containing a polymer compound, wherein the polymer compound comprises a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and the following formula (3): An organic element material which is a polymer compound having at least one repeating unit selected from the group consisting of repeating units represented by:

(1)
[Wherein, R ₁ represents a hydrogen atom or a methyl group. 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. R _aa represents a connecting portion that connects the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. a represents an integer of 0 or 1, and b represents an integer of 1 to 5. When there are a plurality of R, they may be the same or different. When there are a plurality of Rf, they may be the same or different. ]
A repeating unit represented by:

(2)
[Wherein R ₂ represents a hydrogen atom or a methyl group. R _{3 to} R ₉ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group may be substituted with a fluorine atom. R _bb represents a linking moiety that links the main chain and the side chain of the polymer compound. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. ]
A repeating unit represented by:

(3)
[Wherein, R ₁₀ represents a hydrogen atom or a methyl group. R _{11 to} R ₁₇ each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A hydrogen atom in the monovalent organic group 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. A hydrogen atom in the linking moiety may be substituted with a fluorine atom. ]
Repeating unit represented by   An organic thin film transistor insulating layer material comprising the organic element material according to claim 1. Applying a liquid containing the organic element material according to claim 1 onto a surface of a member constituting the organic element to form a coating layer; and irradiating the coating layer with light or an electron beam to form an organic layer. Cross-linking the element material, thereby forming an organic element insulating layer;
The formation method of the organic element insulating layer which has this.   The method for forming an organic element insulating layer according to claim 3, wherein the light has a wavelength of 150 to 450 nm.   The organic thin-film transistor which has an overcoat layer formed using the organic thin-film transistor insulating-layer material of Claim 2.   The organic thin-film transistor which has a gate insulating layer formed using the organic thin-film transistor insulating-layer material of Claim 2.   A display member formed using the organic element material according to claim 1.   A display comprising the display member according to claim 7.

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