JP2007197587A - Composition for electrically conductive material, electrically conductive material, electrically conductive layer, electronic device and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for electrically conductive materials, forming electrically conductive layer of excellent carrier transporting capacity. <P>SOLUTION: The composition for electrically conductive materials contains a compound represented by the formula(A1)[wherein, X is either one of substituents represented by respective formulas(B1) to (B4); and Y is a bivalent aromatic group]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composition for a conductive material, a conductive material, a conductive layer, an electronic device, and an electronic apparatus.

Electroluminescent elements using organic materials (hereinafter simply referred to as “organic EL elements”) are promising for use as solid light-emitting, inexpensive, large-area full-color display elements (light-emitting elements), and many developments have been made. It has been broken.
In general, an organic EL device has a light emitting layer between a cathode and an anode. When an electric field is applied between the cathode and the anode, electrons are injected into the light emitting layer from the cathode side, and holes are formed from the anode side. Is injected.

Then, the injected electrons and holes are recombined in the light emitting layer, and the light emitting layer emits light by releasing the excitation energy when the energy level returns from the conduction band to the valence band as light energy.
In such an organic EL element, in order to increase the efficiency of the organic EL element, that is, to obtain high light emission, an organic layer composed of organic materials having different electron or hole carrier transport properties, and a light emitting layer, It has been found that an element structure laminated between the cathode and / or the anode is effective.

  Therefore, it is necessary to laminate a light emitting layer and an organic layer (hereinafter collectively referred to as “organic layer”) having different carrier transport properties on the electrode. In the manufacturing method using the conventional coating method, When laminating layers, phase dissolution occurs between adjacent organic layers, resulting in a decrease in characteristics such as emission efficiency, color purity or color accuracy of the organic EL element. was there.

Therefore, in the case of stacking organic layers, the organic material is limited to stacking by using a combination of organic materials having different solubility.
As a method for solving such problems, a method for improving the durability of the lower layer, that is, the solvent resistance by polymerizing organic materials constituting the lower organic layer has been disclosed (for example, patents) Reference 1).

Also disclosed is a method for improving the solvent resistance of the lower layer by adding a curable resin to the organic material constituting the lower organic layer and curing it together with the curable resin (for example, patents). Reference 2).
However, even when these methods are used, the actual situation is that the improvement of the characteristics of the organic EL element has not been obtained as expected.
Such a problem also occurs in a thin film transistor using an organic material.

Japanese Patent Laid-Open No. 9-255774 JP 2000-208254 A

  An object of the present invention is to provide a conductive material composition capable of forming a conductive layer having excellent carrier transporting ability, a conductive material having excellent carrier transporting ability obtained by using such a conductive material composition, An object of the present invention is to provide a conductive layer mainly composed of such a conductive material, a highly reliable electronic device, and an electronic apparatus.

［式中、２つのＸは、下記一般式（Ｂ１）〜（Ｂ４）で表される置換基のうちのいずれかを表す。ただし、２つのＸは、その炭素数は、同一であっても、異なっていてもよい。２つのＲ^１は、それぞれ独立して、置換または無置換の一価の芳香族基（ただし、フェニル基を除く。）を表す。４つのＲ^２は、それぞれ独立して、水素原子、メチル基またはエチル基を表す。Ｙは、置換または無置換の下記一般式（Ｃ１）〜（Ｃ３）のうちのいずれかで表される２価の芳香族基を表す。］

［これらの式中、ｎ^１は、２〜８の整数を表し、ｎ^２は、３〜８の整数を表し、ｎ^３は、３〜８の整数を表す。ｍ^１は、０〜３の整数を表し、ｍ^２は、０〜２の整数を表す。Ｚ^１は、水素原子またはメチル基を表し、Ｚ^２は、水素原子、メチル基またはエチル基を表す。］

［これらの式中、ｎ^４は、１〜３の整数を表す。］
これにより、前記一般式（Ａ１）で表される化合物の置換基Ｘ以外の部分である主骨格同士による相互作用を好適に防止して、置換基Ｘを重合反応させて得られた高分子（導電性材料）を優れたキャリア輸送能を発揮するものとすることができる。 Such an object is achieved by the present invention described below.
The composition for conductive materials of the present invention contains a compound represented by the following general formula (A1).

[Wherein, two Xs represent any of substituents represented by the following general formulas (B1) to (B4). However, the two Xs may have the same or different carbon number. Two R ^{1 s} each independently represent a substituted or unsubstituted monovalent aromatic group (excluding a phenyl group). Four R < ² > represents a hydrogen atom, a methyl group, or an ethyl group each independently. Y represents a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) which are substituted or unsubstituted. ]

[In these formulas, n ¹ represents an integer of ² to 8, n ² represents an integer of ³ to 8, and n ³ represents an integer of ³ to 8. m ¹ represents an integer of 0 to 3, and m ² represents an integer of 0 to 2. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

[In these formulas, n ⁴ represents an integer of 1 to 3. ]
Thereby, the polymer (A) obtained by polymerizing the substituent X by suitably preventing the interaction between the main skeletons other than the substituent X of the compound represented by the general formula (A1). The conductive material) can exhibit excellent carrier transport ability.

In the composition for conductive materials of the present invention, the two substituents X preferably have the same carbon number.
Thereby, the separation distance between adjacent main skeletons can be made substantially constant. As a result, it is possible to suitably prevent the electron density from being biased in the polymer, and to reliably improve the carrier transport ability of the polymer.
In the composition for a conductive material of the present invention, the substituent X is preferably bonded to any of the 3-position, 4-position or 5-position of the benzene ring.
Thereby, adjacent main frame | skeletons can be spaced apart more reliably.

In the composition for conductive material of the present invention, the two substituents R ¹ are preferably the same.
As a result, the energy levels and band gaps of the valence band and conduction band of the polymer (prohibited) are preferably prevented while favorably preventing the localization of π electrons in the chemical structure of the conjugated system of the main skeleton. Band width) and the like can be reliably changed, and as a result, the characteristics of the carrier transport ability of the polymer change.

In the composition for conductive material of the present invention, the total number of carbon atoms of the substituent R ¹ is preferably 2 to 30.
By setting the total number of carbon atoms of the substituent R ¹ within such a range, the planarity in the main skeleton can be maintained, and the valence electrons of the polymer can be prevented while reliably preventing the carrier transport ability in the polymer from being lowered. The energy level of the band and the conduction band, the band gap (forbidden band width), and the like can be reliably changed.

In the composition for conductive materials of the present invention, the substituent R ¹ is preferably a monocyclic or condensed polycyclic aromatic group.
This makes it possible to change the energy level, band gap (forbidden band width), and the like of the polymer valence band and conduction band more reliably while maintaining the planarity of the main skeleton more reliably.

［式中、２つのＸは、下記一般式（Ｂ１）〜（Ｂ４）で表される置換基のうちのいずれかを表す。ただし、２つのＸは、その炭素数は、同一であっても、異なっていてもよい。２つのＲ^１は、それぞれ独立して、置換または無置換の一価の芳香族基（ただし、フェニル基を除く。）を表す。４つのＲ^２は、それぞれ独立して、水素原子、メチル基またはエチル基を表す。Ｙは、置換または無置換の下記一般式（Ｃ１）〜（Ｃ３）のうちのいずれかで表される２価の芳香族基を表す。］

［これらの式中、ｎ^１は、２〜８の整数を表し、ｎ^２は、３〜８の整数を表し、ｎ^３は、３〜８の整数を表す。ｍ^１は、０〜３の整数を表し、ｍ^２は、０〜２の整数を表す。Ｚ^１は、水素原子またはメチル基を表し、Ｚ^２は、水素原子、メチル基またはエチル基を表す。］

［これらの式中、ｎ^４は、１〜３の整数を表す。］
これにより、優れたキャリア輸送能を有する導電性材料とすることができる。 The conductive material of the present invention is obtained by polymerizing the compounds represented by the following general formula (A1) in the substituent X.

[Wherein, two Xs represent any of substituents represented by the following general formulas (B1) to (B4). However, the two Xs may have the same or different carbon number. Two R ^{1 s} each independently represent a substituted or unsubstituted monovalent aromatic group (excluding a phenyl group). Four R < ² > represents a hydrogen atom, a methyl group, or an ethyl group each independently. Y represents a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) which are substituted or unsubstituted. ]

[In these formulas, n ¹ represents an integer of ² to 8, n ² represents an integer of ³ to 8, and n ³ represents an integer of ³ to 8. m ¹ represents an integer of 0 to 3, and m ² represents an integer of 0 to 2. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

[In these formulas, n ⁴ represents an integer of 1 to 3. ]
Thereby, it can be set as the electroconductive material which has the outstanding carrier transport ability.

In the conductive material of the present invention, the two substituents X preferably have the same carbon number.
Thereby, the separation distance between adjacent main skeletons can be made substantially constant. As a result, it is possible to suitably prevent the electron density from being biased in the polymer, and to reliably improve the carrier transport ability of the polymer.
In the conductive material of the present invention, the substituent X is preferably bonded to any of the 3-position, 4-position or 5-position of the benzene ring.
Thereby, adjacent main frame | skeletons can be spaced apart more reliably.

In the conductive material of the present invention, the two substituents R ¹ are preferably the same.
As a result, the energy levels and band gaps of the valence band and conduction band of the polymer (prohibited) are preferably prevented while favorably preventing the localization of π electrons in the chemical structure of the conjugated system of the main skeleton. Band width) and the like can be reliably changed, and as a result, the characteristics of the carrier transport ability of the polymer change.

In the conductive material of the present invention, the total number of carbon atoms of the substituent R ¹ is preferably 2 to 30.
By setting the total number of carbon atoms of the substituent R ¹ within such a range, the planarity in the main skeleton can be maintained, and the valence electrons of the polymer can be prevented while reliably preventing the carrier transport ability in the polymer from being lowered. The energy level of the band and the conduction band, the band gap (forbidden band width), and the like can be reliably changed.

In the conductive material of the present invention, the substituent R ¹ is preferably a monocyclic or condensed polycyclic aromatic group.
This makes it possible to change the energy level, band gap (forbidden band width), and the like of the polymer valence band and conduction band more reliably while maintaining the planarity of the main skeleton more reliably.

In the conductive material of the present invention, the compound preferably undergoes a polymerization reaction by light irradiation.
According to the light irradiation, it is possible to relatively easily select a region and a degree of polymerization.
The conductive layer of the present invention is formed using the composition for conductive material of the present invention.
Thereby, the conductive layer excellent in carrier transport ability can be formed.

The conductive layer of the present invention is characterized in that the conductive material of the present invention is a main material.
Thereby, the conductive layer excellent in carrier transport ability can be formed.
In the conductive layer of the present invention, the conductive layer is preferably a hole transport layer.
Thereby, the hole transport layer excellent in hole transport ability can be formed.
In the conductive layer of the present invention, the hole transport layer preferably has an average thickness of 10 to 150 nm.
Thereby, it can be set as the conductive layer which can obtain a highly reliable organic electroluminescent element.

The conductive layer of the present invention is preferably an organic semiconductor layer.
Thereby, the organic-semiconductor layer which shows the outstanding semiconductor characteristic can be formed.
In the conductive layer of the present invention, the average thickness of the organic semiconductor layer is preferably 0.1 to 1000 nm.
Thereby, it can be set as the conductive layer which can obtain a reliable organic thin-film transistor.

The electronic device of the present invention includes the conductive layer of the present invention.
Thereby, an electronic device with high reliability can be obtained.
The electronic device of the present invention is characterized by including a laminate having the conductive layer of the present invention.
Thereby, an electronic device with high reliability can be obtained.
In the electronic device of the present invention, the electronic device is preferably a light emitting element or a photoelectric conversion element.
Thereby, a highly reliable light emitting element and photoelectric conversion element are obtained.

In the electronic device of the present invention, the light emitting element is preferably an organic electroluminescence element.
Thereby, a highly reliable organic electroluminescent element is obtained.
The electronic device of the present invention is characterized by including a laminate having the conductive layer of the present invention.
Thereby, an electronic device with high reliability can be obtained.

The electronic device of the present invention is preferably a switching element.
Thereby, a highly reliable switching element is obtained.
In the electronic device of the present invention, the switching element is preferably an organic thin film transistor.
Thereby, a highly reliable organic thin-film transistor is obtained.
An electronic apparatus according to the present invention includes the electronic device according to the present invention.
Thereby, a highly reliable electronic device can be obtained.

Hereinafter, the composition for conductive material, the conductive material, the conductive layer, the electronic device, and the electronic apparatus of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
<Conductive layer>
First, the conductive layer (the conductive layer of the present invention) composed of the conductive material of the present invention as a main material will be described.

  The conductive material of the present invention is a polymer (polymer) obtained by polymerizing a compound (arylamine derivative) represented by the following general formula (A1) with each other in the substituent X, that is, other than the substituent X. The main component is a polymer formed by linking main skeletons (arylamine skeletons) with a chemical structure formed by the reaction of substituent X (hereinafter, this chemical structure is referred to as “linked structure”). .

［式中、２つのＸは、下記一般式（Ｂ１）〜（Ｂ４）で表される置換基のうちのいずれかを表す。ただし、２つのＸは、その炭素数は、同一であっても、異なっていてもよい。２つのＲ^１は、それぞれ独立して、置換または無置換の一価の芳香族基（ただし、フェニル基を除く。）を表す。４つのＲ^２は、それぞれ独立して、水素原子、メチル基またはエチル基を表す。Ｙは、置換または無置換の下記一般式（Ｃ１）〜（Ｃ３）のうちのいずれかで表される２価の芳香族基を表す。］

[Wherein, two Xs represent any of substituents represented by the following general formulas (B1) to (B4). However, the two Xs may have the same or different carbon number. Two R ^{1 s} each independently represent a substituted or unsubstituted monovalent aromatic group (excluding a phenyl group). Four R < ² > represents a hydrogen atom, a methyl group, or an ethyl group each independently. Y represents a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) which are substituted or unsubstituted. ]

［これらの式中、ｎ^１は、２〜８の整数を表し、ｎ^２は、３〜８の整数を表し、ｎ^３は、３〜８の整数を表す。ｍ^１は、０〜３の整数を表し、ｍ^２は、０〜２の整数を表す。Ｚ^１は、水素原子またはメチル基を表し、Ｚ^２は、水素原子、メチル基またはエチル基を表す。］

[In these formulas, n ¹ represents an integer of ² to 8, n ² represents an integer of ³ to 8, and n ³ represents an integer of ³ to 8. m ¹ represents an integer of 0 to 3, and m ² represents an integer of 0 to 2. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

［これらの式中、ｎ^４は、１〜３の整数を表す。］

[In these formulas, n ⁴ represents an integer of 1 to 3. ]

Here, in such a polymer, the main skeleton is repeatedly bonded through a connecting structure, that is, the main skeleton is repeatedly present at a predetermined distance, Interaction between adjacent main skeletons is reduced.
In addition, the main skeleton has a conjugated chemical structure, and contributes to smooth carrier transport in the polymer by its unique electron cloud spread.

For this reason, this polymer exhibits an excellent carrier transport ability, and a layer comprising such a polymer as a main material has an excellent carrier transport ability.
In such a polymer, if the distance between the main skeletons becomes too short, the interaction between adjacent main skeletons tends to increase, and if the distance between the main skeletons becomes too long, the main skeletons It is difficult to deliver carriers between the two, and the carrier transport ability of the polymer tends to decrease.

From this point of view, it is preferable to set the structure of the substituent X, and the two substituents X are the same among the above general formulas (B1) to (B4). When (B1) or (B2) is selected, a linear carbon-carbon bond having n ¹ of 2 to 8, particularly 3 to 6 is preferred. Also, if you select those above general formula (B3) is, ^{n 2} is 3-8, and, ^{m 1} is linear carbons 0-3 - preferably having a carbon bond, in particular ^{n 2} A linear carbon-carbon bond having 4 to 6 and m ¹ of 1 or 2 is preferable. Furthermore, when the user selects the ones above general formula (B4) is, ^{n 3} is 3-6, and, ^{m 2} linear carbon 0-2 - preferably having a carbon bond, in particular ^{n 3} A linear carbon-carbon bond having 3 to 6 and m ² of 0 is preferable.

Rather than satisfying this relationship, it becomes possible to keep the distance between the main skeletons moderately, and in the polymer, the interaction between adjacent main skeletons can be more reliably reduced, and between the main skeletons Since delivery of the carrier is more reliably performed, the carrier transport ability of the polymer is excellent.
Here, as the substituent X (B1), when you select one of (B2) and (B4) is at its end, respectively, (meth) acryloyl group, an epoxy group, a substituent ^{Z 2} to the vinyl ether groups There are introduced vinyl ether derivative groups. Since (meth) acryloyl group, epoxy group and vinyl ether derivative group have high reactivity and bond stability, they can relatively easily polymerize substituents X to form a polymer having a long chain length. Can do.

  Furthermore, two double bonds (π bonds) exist between the oxygen atom and the carbon atom in the linked structure produced by the polymerization reaction using the (meth) acryloyl group. Thus, even when the distance between the main skeletons is relatively long, the carriers can be reliably transferred between the main skeletons via two π bonds (conjugated bonds). In addition, since a linear carbon-carbon bond (alkylene group) exists between the two π bonds and the main skeleton, enhancement of the interaction between the main skeletons can be prevented.

  An ether bond and a linear carbon-carbon bond (alkylene group) are present in the linked structure produced by the polymerization reaction using an epoxy group or a vinyl ether derivative group. In the connection structure having such a structure, the movement of electrons is suppressed. Thereby, even when the distance between the main skeletons becomes relatively short, it is possible to prevent or suppress the interaction between the main skeletons from increasing.

For example, when there is a structure having many conjugated bonds among π bonds such as a benzene ring, adjacent main skeletons interact with each other through this structure, and the main skeletons are separated from each other. The effect by this will be offset.
However, if you select ones (B3) as a substituent X, the substituents X, as shown in the above general formula (B3), as a functional group at its terminus, introducing a substituent Z ² to the styrene groups Since the styrene derivative group is present, a benzene ring is present in the connection structure.

Therefore, when the benzene ring and the main skeleton having a conjugated chemical structure are too close, for example, when the benzene ring and the main skeleton are bonded by an ether bond, or the total number of n ² and m ¹ is In the case of 2, etc., adjacent main skeletons interact through this benzene ring.
However, in this polymer, the bond between the main skeleton and the benzene ring is formed through a total number of n ² and m ¹ of 3 or more, that is, 3 or more methylene groups and an ether bond. As a result, the distance between the main skeleton and the benzene ring is maintained in a suitable state. As a result, it is possible to suitably suppress or prevent the adjacent main skeletons from interacting with each other.
The substituent Z ² contained in the substituent (B3) and the substituent (B4) is a hydrogen atom, a methyl group or an ethyl group, and the substituent Z ² is n ² and m ¹ or n ³ and m. The total number with ^{2, that} is, the total number of methylene groups may be selected.

For example, wherein when the total number is small, the substituent Z ^2, may be to select a methyl group or an ethyl group. Here, since the methyl group and an ethyl group is an electron donating substituent, as the substituent Z ^2, by selecting the methyl and ethyl groups, it is possible to bias the electrons in the main skeleton side. As a result, it is possible to suitably prevent the adjacent main skeletons from interacting with each other via the benzene ring.

The two substituents X preferably have substantially the same carbon number, and more preferably have the same carbon number. Thereby, the separation distance between adjacent main skeletons can be made substantially constant. As a result, it is possible to suitably prevent the electron density from being biased in the polymer, and to reliably improve the carrier transport ability of the polymer.
The substituent X may be bonded to any position from the 2nd position to the 6th position of the benzene ring, but it is particularly preferable that the substituent X is bonded to any one of the 3rd, 4th and 5th positions. Thereby, the effect of performing the coupling | bonding of adjacent main frame | skeleton via the substituent X can be exhibited more notably. That is, the adjacent main skeletons can be separated more reliably.

Next, the main skeleton contributing to carrier transport in the polymer will be described.
The group (bonding group) Y is a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) that are substituted or unsubstituted. By constituting the group Y with a divalent aromatic group having such a chemical structure, the spread of the electron cloud in the main skeleton is stabilized, and excellent carrier transport ability can be imparted to the main skeleton. As a result, the polymer exhibits excellent carrier transport ability.

Incidentally, ^{n 4} is set within a range of 1-3. By setting the n ⁴ within this range, it is possible to maintain the planarity of the main skeleton, it is possible to reliably obtain the effects as described above.
Here, in the compound (A1), when the substituent R ¹ is composed of a phenyl group, the polymer obtained by polymerizing the compounds (A1) with each other in the substituent X exhibits a hole transporting property. It will be a thing.

On the other hand, the carrier transport in the polymer obtained by constituting the substituent R ¹ with a substituted or unsubstituted monovalent aromatic group (excluding the phenyl group) instead of the phenyl group. Performance characteristics can be easily adjusted. That is, by appropriately selecting the type of the substituted or unsubstituted monovalent aromatic group, for example, the conductive layer of the present invention is applied to the hole transport layer provided in the organic electroluminescence element as described later, and similar. When it is necessary to realize an optimal carrier injection balance for a light emitting material having a skeleton that has different light emission characteristics, that is, in consideration of a combination of a hole transport material and a light emitting material, this hole transport material When it is necessary to control (change) the carrier transport ability of the polymer, the characteristics of the carrier transport ability in the polymer (hole transport material) can be changed relatively easily.
This is because, in the polymer, for example, the energy levels and band gaps of the valence band and the conduction band (the band gap (electron distribution state) of the main skeleton that contributes to carrier transport change. This is thought to be due to the change in the size of the forbidden band.

In addition, instead of constituting the group Y with the above general formulas (C1) to (C3), it is also possible to construct the valence band and conduction band of the polymer by constituting with a divalent aromatic heterocyclic ring other than these. The energy level, band gap (forbidden band width) and the like can be changed. As in the present invention, the type of the substituent R ¹ is changed from a substituted or unsubstituted monovalent aromatic group excluding a phenyl group. By appropriately selecting the configuration, the energy level and band gap (forbidden band width) of the valence band and the conduction band of the polymer can be changed relatively small.

In such a compound (A1), the two substituents R ¹ preferably have substantially the same carbon number, more preferably the same. As a result, the energy levels and band gaps of the valence band and conduction band of the polymer (prohibited) are preferably prevented while favorably preventing the localization of π electrons in the chemical structure of the conjugated system of the main skeleton. Band width) and the like can be changed more reliably, and as a result, the characteristics of the polymer carrier transport ability can be changed more reliably.

The total number of carbon atoms of the substituents ^{R 1} is preferably 2 to 30, more preferably from 2 to 15. By setting the total number of carbon atoms of the substituent R ¹ within such a range, the planarity in the main skeleton can be maintained, and the valence electrons of the polymer can be prevented while reliably preventing the carrier transport ability in the polymer from being lowered. The energy level of the band and the conduction band, the band gap (forbidden band width), and the like can be reliably changed.

The substituent R ¹ is preferably a monocyclic or condensed polycyclic aromatic ring. This makes it possible to change the energy level, band gap (forbidden band width), and the like of the polymer valence band and conduction band more reliably while maintaining the planarity of the main skeleton more reliably.
Considering these, as the substituent R ^1, that is, the substituted or unsubstituted monovalent aromatic group, for example, those represented by the following chemical formulas (D1) to (D9) are particularly preferable structures.

［これらの式中、Ｑ^１は、Ｎ−Ｔ^１、Ｓ、Ｏ、ＳｅまたはＴｅ（ただし、Ｔ^１は、Ｈ、ＣＨ_３またはＰｈを表す。）を表す。Ｑ^２は、Ｎ−Ｔ^３、Ｓ、Ｏ、ＳｅまたはＴｅ（ただし、Ｔ^３は、Ｈ、ＣＨ_３、Ｃ_２Ｈ_５またはＰｈを表す。）を表す。］

[In these formulas, Q ¹ represents NT ¹ , S, O, Se, or Te (where T ¹ represents H, CH _3, or Ph). Q ² represents NT ³ , S, O, Se or Te (where T ³ represents H, CH ₃ , C ₂ H ₅ or Ph). ]

Of these, for example, as a substituent ^{R 1,} the chemical formula (D1), (D3) ~ (D8) ( however, ^{Q 2} is the case of S, Se, or Te) If you select one of a substituted When the group R ¹ is a phenyl group, the energy level of the polymer valence band and conduction band can be increased.
On the other hand, as the substituent R ¹ , any ^one of the above chemical formulas (D2), (D5), (D6), (D8) and (D9) (provided that Q ² is NT ³ or O) When selected, due to the electron-withdrawing effect derived from the skeleton, the energy level of the valence band and conduction band of the polymer can be lowered in comparison with the case where the substituent R ¹ is composed of a phenyl group. it can.

Even if you choose the same substituents R ^1, the substituent R ^1, the nitrogen atom to which the substituent R ¹ is bonded substituent (bonded) position of the polymer by choosing appropriate It is possible to change the energy level of the valence band and the conduction band, the band gap (forbidden band width), and the like.
As described above, by appropriately setting the chemical structure and substitution position of the substituent R ¹ , the energy level and band gap (forbidden band width) of the valence band and the conduction band of the polymer are adjusted to the application. Can be changed (controlled) relatively easily.

In addition, a substituent that does not significantly impair the planarity in the main skeleton may be introduced into the substituent R ¹ . Examples of such a substituent include an alkyl group and a halogen group.
The substituent R ² is a hydrogen atom, a methyl group or an ethyl group, and the substituent R ² may be selected according to the number of carbon atoms of the substituent X. For example, when the number of carbon atoms of the substituent X is large, the substituent R ^2, a hydrogen atom is selected, when the number of carbon atoms of the substituent X is small, the substituent R ^2, a methyl group or ethyl A group may be selected.

  By the way, when a polymer is obtained by advancing the polymerization reaction between the substituents X, a crosslinking agent may be interposed in the polymerization reaction between the substituents X. Accordingly, even when the substituent X having a relatively small carbon number, in other words, a chain having a relatively short chain length is selected, the distance between the main skeletons is preferably too small. It is possible to reliably prevent the interaction between the main skeletons from being increased.

When what is represented by the said general formula (B1) is selected as a substituent X, as a crosslinking agent, a polyester (meth) acrylate crosslinking agent, an epoxy (meth) acrylate crosslinking agent, and a polyurethane (meth) acrylate crosslinking, for example It is preferable to use at least one of acrylic crosslinking agents such as an agent.
In addition, as a polyester (meth) acrylate crosslinking agent, the compound represented by the following general formula (E1)-(E3) is mentioned, for example.
Examples of the epoxy (meth) acrylate crosslinking agent include compounds represented by the following general formulas (E4) to (E8).
As a polyurethane (meth) acrylate crosslinking agent, the compound represented by the following general formula (E9) is mentioned, for example.

［これらの式中、ｎ^５は、４５００以下の整数を表す。ｎ^６は、１〜３の整数を表す。ｎ^７は、０〜１５００の整数を表す。各ｎ^８は、それぞれ独立して、１〜１０の整数を表し、同一であっても、異なっていてもよい。ｎ^９は、１〜４０の整数を表す。ｎ¹⁰は、１〜１００の整数を表す。各Ｒ^３は、それぞれ独立して、炭素数が１〜１０のアルキレン基を表し、同一であっても、異なっていてもよい。Ｒ^４は、炭素数が１〜１００のアルキレン基を表す。各Ａ^１は、それぞれ独立して、水素原子またはメチル基を表し、同一であっても、異なっていてもよい。各Ａ^２は、それぞれ独立して、ジイソシアネート化合物から２つのイソシアネート基を除いた基を表し、同一であっても、異なっていてもよい。］

[In these formulas, n ⁵ represents an integer of 4500 or less. n ⁶ represents represents an integer of 1 to 3. n ⁷ represents an integer of 0 to 1500. Each n ⁸ independently represents an integer of 1 to 10, and may be the same or different. n ⁹ represents an integer of 1 to 40. n ¹⁰ represents an integer of 1 to 100. Each R ³ independently represents an alkylene group having 1 to 10 carbon atoms, and may be the same or different. R ⁴ represents an alkylene group having 1 to 100 carbon atoms. Each A ¹ independently represents a hydrogen atom or a methyl group, and may be the same or different. Each A ² independently represents a group obtained by removing two isocyanate groups from a diisocyanate compound, and may be the same or different. ]

  Moreover, when what is represented by the said general formula (B2) is selected, as a crosslinking agent, (meth) acrylic acid ester type epoxy crosslinking agent, bisphenol type epoxy crosslinking agent, glycidyl ester type epoxy crosslinking agent, fat, for example It is preferable to use at least one of epoxy crosslinking agents such as cyclic epoxy crosslinking agents, urethane-modified epoxy crosslinking agents, silicon-containing epoxy crosslinking agents, polyfunctional phenolic epoxy crosslinking agents and glycidylamine epoxy crosslinking agents. .

In addition, as a (meth) acrylic acid ester type epoxy crosslinking agent, the compound represented by the following general formula (F1) is mentioned, for example.
Examples of the bisphenol type epoxy crosslinking agent include compounds represented by the following general formulas (F2) to (F6).
Examples of the glycidyl ester epoxy crosslinking agent include compounds represented by the following general formulas (F7) to (F8).

Examples of the alicyclic epoxy crosslinking agent include compounds represented by the following general formulas (F9) to (F12).
Examples of the urethane-modified epoxy crosslinking agent include compounds represented by the following general formula (F13).
As a silicon containing epoxy crosslinking agent, the compound represented by the following general formula (F14) is mentioned, for example.
As a polyfunctional phenol type epoxy crosslinking agent, the compound represented by the following general formula (F15)-(F22) is mentioned, for example.
Examples of the glycidylamine-based epoxy crosslinking agent include compounds represented by the following general formulas (F23) to (F25).

［これらの式中、Ａ^１は、水素原子またはメチル基を表す。各ｎ^８は、それぞれ独立して、０〜１０の整数を表し、同一であっても、異なっていてもよい。各ｎ¹¹は、それぞれ独立して、１〜２０の整数を表し、同一であっても、異なっていてもよい。ｎ¹²は、１〜３０の整数を表す。ｎ¹³は、０〜８の整数を表す。Ａ^２は、ジイソシアネート化合物から２つのイソシアネート基を取り除いた基を表し、各Ａ^１は、それぞれ独立して、ジオール化合物から２つの水酸基を取り除いた基を表し、同一であっても異なっていてもよい。］

[In these formulas, A ¹ represents a hydrogen atom or a methyl group. Each n ⁸ independently represents an integer of 0 to 10, and may be the same or different. Each n ¹¹ independently represents an integer of 1 to 20, and may be the same or different. n ¹² represents an integer of 1 to 30. n ¹³ represents an integer of 0-8. A ² represents a group obtained by removing two isocyanate groups from a diisocyanate compound, and each A ¹ independently represents a group obtained by removing two hydroxyl groups from a diol compound, which may be the same or different. Good. ]

  When what is represented by the said general formula (B3) is selected, as a crosslinking agent, a vinyl compound can be used, for example, Among these, the polyethyleneglycol di (G1) represented by the following general formula (G1) It is preferable to use at least one of (meth) acrylate and divinylbenzene.

［式中、ｎ¹⁴は、５〜１５の整数を表し、各Ａ^１は、それぞれ独立して、水素原子またはメチル基を表し、同一であっても、異なっていてもよい。］

[Wherein n ¹⁴ represents an integer of 5 to 15, and each A ¹ independently represents a hydrogen atom or a methyl group, and may be the same or different. ]

Furthermore, when what is represented by the said general formula (B4) is selected, as a crosslinking agent like the case represented by the said general formula (B3), a vinyl compound can be used, for example, It is preferable to use polyethylene glycol di (meth) acrylate represented by the general formula (G1).
Since such a conductive layer is mainly composed of a polymer obtained by a polymerization reaction, it has excellent solvent resistance. As a result, when the upper layer is formed in contact with the conductive layer, it is possible to reliably prevent the conductive layer from swelling or dissolving by the solvent or dispersion medium contained in the material for forming the upper layer. it can.

  In addition, when an electronic device as will be described later is constructed using a laminate having such a conductive layer, the layer that comes into contact with the conductive layer because the conductive layer is composed mainly of a polymer. In the vicinity of the interface of the (contact layer), it is possible to reliably prevent the constituent material of the conductive layer and the constituent material of the contact layer from being mixed with time. As a result, it is possible to prevent the characteristics of the electronic device from deteriorating with time.

<Organic electroluminescence device>
Next, an embodiment in which the electronic device of the present invention is applied to an organic electroluminescence element (hereinafter simply referred to as “organic EL element”) which is a light emitting element will be described.
FIG. 1 is a longitudinal sectional view showing an example of an organic EL element.
An organic EL element 1 shown in FIG. 1 includes a transparent substrate 2, an anode 3 provided on the substrate 2, an organic EL layer 4 provided on the anode 3, and a cathode provided on the organic EL layer 4. 5 and a protective layer 6 provided so as to cover each of the layers 3, 4, and 5.

The substrate 2 serves as a support for the organic EL element 1, and each of the layers is formed on the substrate 2.
As a constituent material of the substrate 2, a material having translucency and good optical characteristics can be used.
Examples of such materials include various resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, and various glass materials. And at least one of these can be used.

Although the thickness (average) of the board | substrate 2 is not specifically limited, It is preferable that it is about 0.1-30 mm, and it is more preferable that it is about 0.1-10 mm.
The anode 3 is an electrode that injects holes into the organic EL layer 4 (a hole transport layer 41 described later). The anode 3 is substantially transparent (colorless transparent, colored transparent, translucent) so that light emission from the organic EL layer 4 (light emitting layer 42 described later) can be visually recognized.

From such a viewpoint, as the constituent material (anode material) of the anode 3, it is preferable to use a material having a large work function, excellent conductivity, and translucency.
Examples of such an anode material include ITO (Indium Tin Oxide), SnO ₂ , Sb-containing SnO ₂ , oxides such as Al-containing ZnO, Au, Pt, Ag, Cu, or alloys containing these, and the like. At least one of these can be used.

  The thickness (average) of the anode 3 is not particularly limited, but is preferably about 10 to 200 nm, and more preferably about 50 to 150 nm. If the thickness of the anode 3 is too thin, the function as the anode 3 may not be sufficiently exhibited. On the other hand, if the anode 3 is too thick, the light transmittance may be remarkably lowered depending on the type of anode material. There is a risk that it will not be suitable for practical use.

As the anode material, for example, a conductive resin material such as polythiophene or polypyrrole can be used.
On the other hand, the cathode 5 is an electrode for injecting electrons into the organic EL layer 4 (an electron transport layer 43 described later).
As a constituent material (cathode material) of the cathode 5, it is preferable to use a material having a small work function.

Examples of such cathode materials include Li, Mg, Ca, Sr, La, Ce, Er, Eu, Sc, Y, Yb, Ag, Cu, Al, Cs, Rb, and alloys containing these, and the like. At least one of them can be used.
In particular, when an alloy is used as the cathode material, an alloy containing a stable metal element such as Ag, Al, or Cu, specifically, an alloy such as MgAg, AlLi, or CuLi is preferably used. By using such an alloy as the cathode material, the electron injection efficiency and stability of the cathode 5 can be improved.

The thickness (average) of the cathode 5 is preferably about 1 nm to 1 μm, and more preferably about 100 to 400 nm. If the thickness of the cathode 5 is too thin, the function as the cathode 5 may not be sufficiently exhibited. On the other hand, if the cathode 5 is too thick, the light emission efficiency of the organic EL element 1 may be reduced.
An organic EL layer (organic layer) 4 is provided between the anode 3 and the cathode 5. The organic EL layer 4 includes a hole transport layer 41, a light emitting layer 42, and an electron transport layer 43, which are formed on the anode 3 in this order.

The hole transport layer 41 has a function of transporting holes injected from the anode 3 to the light emitting layer 42.
As the hole transport layer 41, the conductive material of the present invention can be used.
Here, when the hole transport layer 41 is formed using the conductive material of the present invention as a main material, for example, depending on the light emission characteristics of the constituent material (light emitting material) of the light emitting layer 42 described later, that is, red, green or The constituent material of the hole transport layer 41 may be selected in consideration of the carrier injection balance (characteristic of carrier transport ability) of the conductive material of the present invention as described above according to the difference in emission color such as blue.

That is, when the electron injection efficiency from the electron transport layer 43 described later to the light emitting layer 42 is relatively low, the hole injection efficiency from the hole transport layer 41 to the light emitting layer 42 can be somewhat suppressed. A constituent material of the hole transport layer 41 may be selected.
Specifically, when it is desired to slightly suppress the hole injection efficiency, for example, as a conductive material used for the hole transport layer 41, the chemical structure of the substituent R ¹ has the chemical formulas (D2), (D5), ( D6), (D8) and (D9) (however, ^{Q 2} is preferably selected one of the case of the ^{N-T 3} or O). Thereby, the effects as described above can be obtained with certainty.

On the other hand, when the electron injection efficiency from the electron transport layer 43 to the light emitting layer 42 is relatively high, the hole injection efficiency from the hole transport layer 41 to the light emitting layer 42 can be slightly promoted. In addition, the constituent material of the hole transport layer 41 may be selected.
Specifically, when it is desired to slightly promote the hole injection efficiency, for example, as the conductive material used for the hole transport layer 41, the chemical structure of the substituent R ¹ has the chemical formulas (D1), (D3) to (D8). ) (Provided that Q ² is S, Se or Te). Thereby, the effects as described above can be obtained with certainty.
Further, the hole transport layer 41 preferably has a volume resistivity of 10 Ω · cm or more, more preferably 10 ² Ω · cm or more. Thereby, the organic EL element 1 with higher luminous efficiency can be obtained.

The thickness (average) of the hole transport layer 41 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm. If the thickness of the hole transport layer 41 is too thin, pinholes may be generated. On the other hand, if the hole transport layer 41 is too thick, the transmittance of the hole transport layer 41 may be deteriorated, resulting in an organic EL element. There is a possibility that the chromaticity (hue) of the emission color of 1 will change.
The conductive material of the present invention is particularly useful when such a relatively thin hole transport layer 41 is formed.
The electron transport layer 43 has a function of transporting electrons injected from the cathode 5 to the light emitting layer 42.

As a constituent material (electron transport material) of the electron transport layer 43, for example, 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1), 1, Benzene compounds (starburst compounds) such as 3,5-tris [{3- (4-t-butylphenyl) -6-trisfluoromethyl} quinoxalin-2-yl] benzene (TPQ2), such as naphthalene Naphthalene compounds, phenanthrene compounds such as phenanthrene, chrysene compounds such as chrysene, perylene compounds such as perylene, anthracene compounds such as anthracene, pyrene compounds such as pyrene, acridines such as acridine Compounds, stilbene compounds such as stilbene, thiophene such as BBOT Compounds, butadiene compounds such as butadiene, coumarin compounds such as coumarin, quinoline compounds such as quinoline, bistyryl compounds such as bistyryl, pyrazine compounds such as pyrazine and distyrylpyrazine, quinoxaline Quinoxaline compounds, benzoquinone, benzoquinone compounds such as 2,5-diphenyl-para-benzoquinone, naphthoquinone compounds such as naphthoquinone, anthraquinone compounds such as anthraquinone, oxadiazole, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD), oxadiazole compounds such as BMD, BND, BDD, BAPD, triazole, 3,4,5-tri Phenyl-1,2,4-triazol Triazole compounds such as oxazole compounds, anthrone compounds such as anthrone, fluorenone, fluorenone compounds such as 1,3,8-trinitro-fluorenone (TNF), diphenoquinone, diphenoquinone compounds such as MBDQ, Stilbenequinone, stilbenequinone compounds such as MBSQ, anthraquinodimethane compounds, thiopyran dioxide compounds, fluorenylidenemethane compounds, diphenyldicyanoethylene compounds, fluorene compounds such as fluorene, phthalocyanine, copper phthalocyanine, metal or metal-free phthalocyanine compound such as iron phthalocyanine, (8-hydroxyquinoline) aluminum (Alq _3), a a ligand benzoxazole or benzothiazole Various metal complexes such as the body thereof.

Moreover, at least 1 sort (s) of the above compounds can be used for an electron transport material.
Furthermore, the thickness (average) of the electron transport layer 43 is not particularly limited, but is preferably about 1 to 100 nm, and more preferably about 20 to 50 nm. If the thickness of the electron transport layer 43 is too thin, pinholes may occur and short circuit may occur, while if the electron transport layer 43 is too thick, the resistance value may increase.

  When the anode 3 and the cathode 5 are energized (voltage is applied), holes move in the hole transport layer 41 and electrons move in the electron transport layer 43. The electrons recombine. In the light emitting layer 42, excitons (excitons) are generated by the energy released upon this recombination, and energy (fluorescence or phosphorescence) is emitted (emitted) when the excitons return to the ground state.

As a constituent material (light emitting material) of the light emitting layer 42, holes can be injected from the anode 3 side when electrons are applied, and electrons can be injected from the cathode 5 side, thereby providing a field where holes and electrons recombine. Any thing can be used as long as it is possible.
Such light-emitting materials include various low-molecular light-emitting materials and various high-molecular light-emitting materials as described below, and at least one of these can be used.

  In addition, since the dense light emitting layer 42 is obtained by using a low molecular light emitting material, the light emission efficiency of the light emitting layer 42 is improved. In addition, since the polymer light-emitting material can be dissolved in a solvent relatively easily, the light-emitting layer 42 can be easily formed by various coating methods such as an ink jet printing method. Furthermore, by using a combination of a low-molecular light-emitting material and a high-molecular light-emitting material, the light-emitting layer has the effect of using a low-molecular light-emitting material and a high-molecular light-emitting material. 42 can be easily formed by various coating methods such as an ink jet printing method.

Examples of low-molecular light-emitting materials include benzene compounds such as distyrylbenzene (DSB) and diaminodistyrylbenzene (DADSB), naphthalene compounds such as naphthalene and nile red, and phenanthrene compounds such as phenanthrene. Chrysene, chrysene compounds such as 6-nitrochrysene, perylene, N, N′-bis (2,5-di-t-butylphenyl) -3,4,9,10-perylene-di-carboximide (BPPC) Perylene compounds such as coronene, anthracene compounds such as anthracene and bisstyrylanthracene, pyrene compounds such as pyrene, 4- (di-cyanomethylene) -2-methyl-6 Such as-(para-dimethylaminostyryl) -4H-pyran (DCM) Pyran compounds, acridine compounds such as acridine, stilbene compounds such as stilbene, thiophene compounds such as 2,5-dibenzoxazole thiophene, benzoxazole compounds such as benzoxazole, benzos such as benzimidazole Imidazole compounds, benzothiazole compounds such as 2,2 '-(para-phenylenedivinylene) -bisbenzothiazole, bistyryl (1,4-diphenyl-1,3-butadiene), butadienes such as tetraphenylbutadiene Compounds, naphthalimide compounds such as naphthalimide, coumarin compounds such as coumarin, perinone compounds such as perinone, oxadiazole compounds such as oxadiazole, aldazine compounds, 1, 2, 3 , 4, Cyclopentadiene compounds such as 5-pentaphenyl-1,3-cyclopentadiene (PPCP), quinacridone compounds such as quinacridone and quinacridone red, pyridine compounds such as pyrrolopyridine and thiadiazolopyridine, 2,2 Spiro compounds such as', 7,7'-tetraphenyl-9,9'-spirobifluorene, phthalocyanine (H ₂ Pc), metal or non-metal phthalocyanine compounds such as copper phthalocyanine, florene such as fluorene Compounds, (8-hydroxyquinoline) aluminum (Alq ₃ ), tris (4-methyl-8quinolinolate) aluminum (III) (Almq ₃ ), (8-hydroxyquinoline) zinc (Znq ₂ ), (1,10- Phenanthroline) -tris- (4,4,4-trif Oro-1- (2-thienyl) - butane-1,3-Jioneto) europium _{(III) (Eu (TTA)} 3 (phen)), factory scan (2-phenylpyridine) iridium (Ir _(ppy) 3), Examples include (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-porphine) various metal complexes such as platinum (II).

  Examples of the polymer light-emitting material include polyacetylene compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), poly (alkyl, phenylacetylene) (PAPA), and poly (para-para-). Fenvinylene) (PPV), poly (2,5-dialkoxy-para-phenylenevinylene) (RO-PPV), cyano-substituted-poly (para-phenvinylene) (CN-PPV), poly (2-dimethyloctyl) Polyparaphenylene vinylene compounds such as silyl-para-phenylene vinylene (DMOS-PPV), poly (2-methoxy, 5- (2′-ethylhexoxy) -para-phenylene vinylene) (MEH-PPV), poly ( 3-alkylthiophene) (PAT), poly (oxypropylene) Polythiophene compounds such as riol (POPT), poly (9,9-dialkylfluorene) (PDAF), α, ω-bis [N, N′-di (methylphenyl) aminophenyl] -poly [9,9- Bis (2-ethylhexyl) fluorene-2,7-diyl] (PF2 / 6am4), poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) Polyfluorene compounds such as poly (para-phenylene) (PPP), polyparaphenylene compounds such as poly (1,5-dialkoxy-para-phenylene) (RO-PPP), poly (N-vinyl) Polycarbazole compounds such as carbazole (PVK), poly (methylphenylsilane) (PMPS), poly (naphthylphenylsilane) PnPs), polysilane-based compounds such as poly (biphenylyl phenyl silane) (pBPS), and the like.

Further, depending on the combination of constituent materials used for the hole transport layer 41 and the electron transport layer 43, the conductive material of the present invention can be used as the light emitting material.
For example, as a constituent material of the hole transport layer 41, poly (thiophene / styrenesulfonic acid) such as poly (3,4-ethylenedioxythiophene / styrenesulfonic acid), N, N′-bis (1-naphthyl) An arylamine compound such as —N, N′-diphenyl-benzidine (α-NPD) is used, and the electron transport layer 43 is made of a material such as 3,4,5-triphenyl-1,2,4-triazole. Triazole compounds, oxadiazole compounds such as 2- (4-t-butylphenyl) -5- (biphenyl-4-yl) -1,3,5-oxadiazole (PBD), etc. the, as the conductive material constituting the emitting layer 42, for example, may be a chemical structure of the substituents R ¹ is used as the chemical formula (D2).

The thickness (average) of the light emitting layer 42 is not particularly limited, but is preferably about 10 to 150 nm, and more preferably about 50 to 100 nm. By setting the thickness of the light emitting layer in the above range, recombination of holes and electrons is efficiently performed, and the light emission efficiency of the light emitting layer 42 can be further improved.
The organic EL element 1 may be such that either one of the hole transport layer 41 or the light emitting layer 42 is composed of the conductive material of the present invention, both of which are those of the present invention. It may be composed of a conductive material.

  In addition, the light emitting layer 42 is provided separately from the hole transport layer 41 and the electron transport layer 43, but a hole transportable light emitting layer that serves as the hole transport layer 41 and the light emitting layer 42, or an electron transport layer An electron-transporting light-emitting layer that also serves as the light-emitting layer 43 and the light-emitting layer 42 can be used. In this case, the vicinity of the interface between the hole-transporting light-emitting layer and the electron-transporting layer 43 and the vicinity of the interface between the electron-transporting light-emitting layer and the hole-transporting layer 41 function as the light-emitting layer.

Furthermore, when a hole transporting light emitting layer is used, holes injected from the anode into the hole transporting light emitting layer are confined by the electron transport layer, and when an electron transporting light emitting layer is used, Since electrons injected from the cathode into the electron-transporting light-emitting layer are confined in the electron-transporting light-emitting layer, both have the advantage that the recombination efficiency between holes and electrons can be improved.
An arbitrary target layer may be provided between the layers 3, 4, and 5. For example, a hole injection layer that improves the efficiency of hole injection from the anode 3 can be provided between the hole transport layer 41 and the anode 3. Thus, when providing a positive hole injection layer in the organic EL element 1, the conductive material of this invention can be used as a constituent material of this positive hole injection layer.

  Further, an electron injection layer or the like for improving the efficiency of electron injection from the cathode 5 can be provided between the electron transport layer 43 and the cathode 5. As a constituent material of the hole injection layer, in addition to the conductive material of the present invention, for example, copper phthalocyanine or 4,4 ′, 4 ″ -tris (N, N-phenyl-3-methylphenylamino) triphenylamine (M-MTDATA) or the like can be used.

The protective layer 6 is provided so as to cover the layers 3, 4, and 5 constituting the organic EL element 1. The protective layer 6 has a function of hermetically sealing the layers 3, 4, and 5 constituting the organic EL element 1 and blocking oxygen and moisture. By providing the protective layer 6, it is possible to obtain the effects of improving the reliability of the organic EL element 1 and preventing deterioration and deterioration.
Examples of the constituent material of the protective layer 6 include Al, Au, Cr, Nb, Ta, Ti, alloys containing these, silicon oxide, various resin materials, and the like. In addition, when using the material which has electroconductivity as a constituent material of the protective layer 6, in order to prevent a short circuit, between the protective layer 6 and each layer 3, 4, 5 as needed, an insulating film Is preferably provided.

The organic EL element 1 can be used, for example, for a display, but can also be used as a light source or the like, and can be used for various optical applications.
Further, when the organic EL element 1 is applied to a display, the driving method is not particularly limited, and either an active matrix method or a passive matrix method may be used.
Such an organic EL element 1 can be manufactured as follows, for example.

[A1] Anode Formation Step First, the substrate 2 is prepared, and the anode 3 is formed on the substrate 2.
The anode 3 is, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, or a wet method such as electrolytic plating, immersion plating, or electroless plating. It can be formed by using a plating method, a thermal spraying method, a sol-gel method, a MOD method, a metal foil bonding, or the like.

[A2] Hole transport layer forming step (first configuration)
[A2-1] First, a composition for a conductive material (hole transport material) containing a compound represented by the general formula (A1) (hereinafter, simply referred to as “compound (A1)”) is placed on the anode 3. Apply (supplied).
For this coating, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, Various coating methods such as an offset printing method and an ink jet printing method can be used. According to such a coating method, the hole transport material can be supplied onto the anode 3 relatively easily.

  When the compound (A1) is dissolved in a solvent or dispersed in a dispersion medium, examples of the solvent or dispersion medium to be used include inorganic solvents such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, and ethylene carbonate, Ketone solvents such as methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol (DEG), glycerin Solvent, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ester Ether solvents such as ether (diglyme), diethylene glycol ethyl ether (carbitol), cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, toluene, Aromatic hydrocarbon solvents such as xylene and benzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide Amide solvents such as (DMA), halogen compound solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate, ethyl formate, dimethyl sulfoxide (DMSO), Various organic solvents such as sulfur compound solvents such as ruphoran, nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or a mixture containing these A solvent etc. are mentioned.

In addition, it is preferable to add a polymerization initiator to the composition for conductive materials. Thereby, in the next step [A2-2], when a predetermined treatment such as heating or light irradiation is performed, the polymerization reaction in the substituent X can be promoted.
Although it does not specifically limit as a polymerization initiator, For example, photopolymerization initiators, such as a photocationic polymerization initiator and a radical photopolymerization initiator, a thermal polymerization initiator, an anaerobic polymerization initiator, etc. are mentioned.

In addition, when what is represented by the said general formula (B1) or the said general formula (B3) is selected as a substituent X, it is especially preferable to use a radical photopolymerization initiator as a polymerization initiator.
As the photoradical polymerization initiator, various photoradical polymerization initiators can be used. Photoradical polymerization initiators such as those based on xanthene, xanthene and thioxanthone can be used.

Moreover, when the thing represented by the said general formula (B2) or the said general formula (B4) is selected as a substituent X, it is especially preferable to use a photocationic polymerization initiator as a polymerization initiator.
As the cationic photopolymerization initiator, various kinds of cationic photopolymerization initiators can be used. For example, aromatic sulfonium salt type, aromatic iodonium salt type, aromatic diazonium salt type, pyridium salt type and aromatic phosphonium salt. An onium salt-based photocationic polymerization initiator such as a non-ionic photocationic polymerization initiator such as an iron arene complex or a sulfonic acid ester can be used.

By appropriately selecting the polymerization initiator as described above according to the type of the substituent X to be selected, in the next step [A2-2], the substituent X can be polymerized relatively easily.
In addition, when using a photoinitiator as a polymerization initiator, you may add the sensitizer suitable for a photoinitiator to the composition for electroconductive materials.

[A2-2] Next, the hole transport material supplied onto the anode 3 is irradiated with light.
Thereby, the polymer (conductive material of the present invention) in which the compounds (A1) contained in the hole transport material are subjected to a polymerization reaction in the substituent X can be obtained. As a result, a hole transport layer 41 mainly composed of the conductive material of the present invention is formed on the anode 3.
By configuring the hole transport layer 41 as the main material of the conductive material of the present invention, when the light emitting layer material is supplied in the next step [A3], the solvent or dispersion medium contained in the light emitting layer material It is possible to prevent the hole transport layer 41 from swelling and dissolving. As a result, phase dissolution of the hole transport layer 41 and the light emitting layer 42 can be reliably prevented.

Moreover, in the organic EL element 1 obtained by constituting the hole transport layer 41 with the conductive material (polymer) of the present invention as a main material, in the vicinity of the interface between the hole transport layer 41 and the light emitting layer 42. These constituent materials can be reliably prevented from being mixed with time.
The weight average molecular weight of the polymer is not particularly limited, but is preferably about 10,000 to 1,000,000, more preferably about 15,000 to 300,000. Thereby, swelling and dissolution of the polymer can be suppressed or prevented more reliably.

The hole transport layer 41 may contain a low molecule (monomer or oligomer) of the compound (A1) as long as the phase dissolution between the hole transport layer 41 and the light emitting layer 42 is prevented.
Examples of the light that irradiates the hole transport material include infrared rays, visible rays, ultraviolet rays, and X-rays, and one or more of these can be used in combination. Among these, it is particularly preferable to use ultraviolet rays. Thereby, the polymerization reaction in the substituent X can be easily and reliably advanced.

When the substituent X is selected from those represented by the general formula (B1) or the general formula (B3), the wavelength of the ultraviolet rays to be irradiated is preferably about 100 to 420 nm, preferably about 150 to 400 nm. It is more preferable that
The irradiation intensity of ultraviolet light is preferably in the range of about 1~600mW / cm ^2, more preferably about 1~300mW / cm ^2.

Furthermore, the irradiation time of ultraviolet rays is preferably about 60 to 600 seconds, and more preferably about 90 to 500 seconds.
In addition, when the substituent X is selected from those represented by the general formula (B2) or the general formula (B4), the wavelength of ultraviolet rays to be irradiated is preferably about 200 to 420 nm, preferably 250 to More preferably, it is about 400 nm.

The irradiation intensity of ultraviolet light is preferably in the range of about 10~5000mW / cm ^2, more preferably about 20 to 1000 mW / cm ^2.
Furthermore, the ultraviolet irradiation time is preferably about 5 to 300 seconds, and more preferably about 10 to 150 seconds.
Depending on the type of substituent X to be selected, the progress of the polymerization reaction of the hole transport material supplied onto the anode 3 can be controlled relatively easily by setting the wavelength, irradiation intensity, and irradiation time of the ultraviolet ray within such a range. can do.

[2 ′] Hole transport layer forming step (second configuration)
Moreover, when what is represented by the said general formula (B4) is selected as a substituent X, you may make it form a positive hole transport layer by the process as shown below.
[2′-1] First, the compound (A1) is dissolved in a reaction solvent capable of dissolving the compound (A1) to obtain a composition for a conductive material.

  As the reaction solvent, the same solvent or dispersion medium as described in the above step [2-1] can be used. However, among those described in the above step [2-1], a comparison such as an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an aromatic heterocyclic compound solvent, a halogen compound solvent, and a sulfur compound solvent. It is preferable to select those with weak basicity. Thereby, the polymerization of the compound (A1) in the next step [2′-2] can be surely proceeded without being inhibited by the selected reaction solvent. Among these, it is particularly preferable to select one having a small dielectric constant. Thereby, the polymerization rate of the polymerization of the compound (A1) is reduced, and a polymer having a relatively small molecular weight can be easily obtained. Therefore, the control of the molecular weight of the resulting polymer of the compound (A1) is relatively controlled. It can be done easily.

[2′-2] Next, the compounds (A1) contained in the composition for conductive materials are subjected to a polymerization reaction in the substituent X, so that a polymer (soluble polymer) of the compound (A1) is contained in the reaction solvent. The compound (A1) is polymerized to a soluble range.
At this time, by adding a polymerization catalyst to the composition for conductive material, the polymerization reaction in the substituent X, that is, the polymerization of the compound (A1) can be promoted.

  The weight average molecular weight of the polymer (soluble polymer) of such a compound (A1) is slightly different depending on the type of the compound (A1) and is not particularly limited, but is preferably about 800 to 10,000. More preferably, it is about 1500 to 5000. Thereby, it can prevent reliably that the polymer of a compound (A1) insolubilizes and deposits (precipitate) in the composition for electroconductive materials.

Such a polymer of the compound (A1) is obtained by subjecting the composition for a conductive material to predetermined treatment such as reaction temperature control, light irradiation, and anaerobic treatment in the presence of a polymerization catalyst. Can do.
The polymerization reaction between the compounds (A1) can be controlled relatively easily by appropriately setting the conditions for the predetermined treatment. Therefore, before the insoluble polymer is formed, that is, before the polymer formed by the progress of the polymerization reaction is insolubilized, the polymerization of the compound (A1) can be reliably stopped.

As the predetermined treatment, it is preferable to select control of the reaction temperature among the above-mentioned treatments. Polymerization of the compound (A1) can be more easily controlled by appropriately setting the treatment conditions for controlling the reaction temperature.
The temperature of the composition for conductive material when controlling the reaction temperature is slightly different depending on the kind of the reaction solvent described above, but is preferably about −78 to 25 ° C., and is about −40 to 0 ° C. Is more preferable.

The time for controlling the reaction temperature also varies slightly depending on the kind of the reaction solvent described above, but is preferably about 0.5 to 24 hours, more preferably about 1 to 5 hours.
By controlling the temperature of the composition for conductive material and the time for controlling the reaction temperature in such a range, the compound (A1) can be polymerized without insolubilization.
In addition, when the polymer (soluble polymer) of a compound (A1) is obtained, you may make it add a polymerization terminator to the composition for electroconductive materials. Thereby, high molecularization of a compound (A1) can be stopped more reliably.
Examples of such a polymerization terminator include lower alcohols such as methanol, ethanol and isopropyl alcohol containing a basic compound such as aqueous ammonia, and ether solvents such as diethyl ether and tetrahydrofuran.

The polymerization catalyst is not particularly limited. For example, protonic acids such as halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, and phosphoric acid monoester, boron trifluoride, boron trifluoride etherate (BF ₃ / OEt ₂ ), titanium dichloride, titanium tetrachloride, stannous chloride, stannic chloride, aluminum chloride, zinc chloride, magnesium bromide, ferric chloride and the like. However, when a Lewis acid is used as a polymerization catalyst, it is preferable to add a compound having unpaired electrons such as water, alcohol, carboxylic acid, and ether as a cocatalyst to the conductive material composition. Thereby, high molecularization of a compound (A1) can be performed more reliably.

[2′-3] Next, impurities other than the polymer (soluble polymer) of the compound (A1) contained in the conductive material composition are removed from the conductive composition.
As this impurity, for example, a low-molecular compound (monomer or oligomer) of compound (A1), a polymerization catalyst, a cocatalyst, a product generated and / or mixed when synthesizing compound (A1), and a compound mixed in a reaction solvent Etc.

  Such impurities are classified as cationic, anionic and nonionic impurities. Among these, examples of methods for removing cationic and anionic impurities include filtration methods, adsorption chromatography methods and ion exchange chromatography methods. Among these methods, filtration methods are used. It is preferable to use it. According to the filtration method, the target cationic impurities and anionic impurities can be efficiently and reliably removed by simply selecting the type of filter to be used.

That is, as a filter, for example, a material composed mainly of a cation exchange resin such as a strong acid cation exchange resin, a weak acid cation exchange resin, or a chelate resin capable of selectively removing heavy metals is selected. Thus, cationic impurities can be removed.
In addition, as a filter, for example, an anion exchange resin such as the strongest basic anion exchange resin, strong basic anion exchange resin, medium basic anion exchange resin, weak basic anion exchange resin, etc. is used as a main material. By selecting a constituent, anionic impurities can be removed.

  Examples of the method for removing nonionic impurities include an ultrafiltration membrane method and a gel permeation chromatography method. Among these, the ultrafiltration membrane method is preferably used. The ultrafiltration membrane method is excellent in the separation characteristics of various substances according to the molecular weight, and by simply selecting the type of ultrafiltration membrane to be used, nonionic impurities smaller than the target molecular weight can be removed efficiently and reliably. can do.

[2′-4] Next, a conductive material composition containing a polymer (soluble polymer) of the compound (A1) is applied (supplied) onto the anode 3.
For this coating, the same method as described in the above step [2-1] can be used.
In addition, it is preferable to add a polymerization initiator to this composition for conductive materials. Thereby, in the next step [2′-5], when a predetermined treatment such as heating or light irradiation is performed, the polymerization reaction in the substituent X between the polymers of the compound (A1) can be promoted.
As this polymerization initiator, the same ones as described in the above step [2-1] can be used.

[2′-5] Next, the composition for conductive material supplied onto the anode 3 is irradiated with light.
Thereby, the polymer of the compound (A1) contained in the composition for conductive materials can be subjected to a polymerization reaction in the substituent X. Thereby, the polymer (soluble polymer) of the compound (A1) is further insolubilized by being polymerized, and is precipitated in the composition for conductive material. As a result, the hole transport layer 41 mainly composed of the polymer (insoluble polymer) of the compound (A1), that is, the conductive material of the present invention is formed on the anode 3.

The weight average molecular weight of the polymer (insoluble polymer) of this compound (A1) is not particularly limited, but is preferably about 15,000 to 1,000,000, and more preferably about 20,000 to 300,000. Thereby, swelling and dissolution of the polymer can be suppressed or prevented more reliably.
As the light for irradiating the composition for conductive material, the same light as described in the step [2-2] can be used.

  The hole transport layer 41 is formed through the process [2 '] as described above. By forming the hole transport layer 41 by such a step, the polymer (soluble polymer) of the compound (A1) is added to the conductive material composition supplied onto the anode 3 in the step [2′-5]. Therefore, the addition amount of the polymerization initiator can be set relatively small. As a result, the amount of the polymerization initiator remaining in the obtained hole transport layer 41 is relatively small. Thereby, since the hole in the hole transport layer 41 can be suitably prevented or suppressed from being trapped by the polymerization initiator, the hole transport layer 41 to be obtained exhibits excellent hole transport ability. be able to.

In the method [2 ′], after the polymer (soluble polymer) of the compound (A1) is supplied onto the anode 3, the polymer is further insolubilized by polymerizing the hole transport layer 41. Since the hole transport layer 41 is formed, there is an advantage that a uniform film having a narrow molecular weight distribution can be formed (film formation) relatively easily.
Note that the obtained hole transport layer 41 may be subjected to heat treatment, for example, in the air, in an inert atmosphere, or under reduced pressure (or vacuum), if necessary. Thereby, for example, the hole transport layer 41 can be dried and solidified (desolvent or dedispersion medium). The hole transport layer 41 may be dried regardless of heat treatment.
In addition to the light irradiation described in the step [2-2] and the step [2′-5], examples of the predetermined treatment for causing the polymerization reaction in the substituent X include heating and anaerobic treatment. Among these, it is preferable to use light irradiation. According to the light irradiation, it is possible to relatively easily select a region and a degree of polymerization.

[A3] Light-Emitting Layer Formation Step Next, the light-emitting layer 42 is formed on the hole transport layer 41.
The light emitting layer 42 is formed, for example, by applying a light emitting layer material (light emitting layer forming material) obtained by dissolving the above light emitting material in a solvent or dispersing in a dispersion medium on the hole transport layer 41. Can do.
As the solvent or dispersion medium for dissolving or dispersing the light emitting material, the same solvent or dispersion medium used when forming the hole transport layer 41 can be used.
Further, as a method of applying the light emitting layer material on the hole transport layer 41, the same method as that used when forming the hole transport layer 41 can be used.

[A4] Electron Transport Layer Formation Step Next, the electron transport layer 43 is formed on the light emitting layer 42.
The electron transport layer 43 is formed in the same manner as the light emitting layer forming step [A3] except that the above electron transport material is used instead of the light emitting material.
In addition, when the light emitting layer 42 is not comprised with polymers like the electroconductive material of this invention, the solvent or dispersion medium for melt | dissolving or disperse | distributing the composition for electroconductive materials used in order to form the electron carrying layer 43 For example, the light emitting layer 42 may be selected so that it does not swell and dissolve. Thereby, phase dissolution of the light emitting layer 42 and the electron transport layer 43 can be reliably prevented.

[A5] Cathode Formation Step Next, the cathode 5 is formed on the electron transport layer 43.
The cathode 5 can be formed using, for example, a vacuum deposition method, a sputtering method, a metal foil bonding, or the like.
[A6] Protective Layer Formation Step Next, the protective layer 6 is formed so as to cover the anode 3, the organic EL layer 4, and the cathode 5.
The protective layer 6 can be formed (provided), for example, by bonding a box-shaped protective cover made of the above-described material with various curable resins (adhesives).
As the curable resin, any of a thermosetting resin, a photocurable resin, a reactive curable resin, and an anaerobic curable resin can be used.
The organic EL element 1 is manufactured through the above processes.

<Organic thin film transistor>
Next, an embodiment in which the electronic device of the present invention is applied to an organic thin film transistor (hereinafter simply referred to as “organic TFT”) as a switching element will be described.
2A and 2B are diagrams showing the organic TFT 10, in which FIG. 2A is a longitudinal sectional view and FIG. 2B is a plan view. In the following description, the upper side in FIG. 2A is referred to as “upper” and the lower side is referred to as “lower”.
The organic TFT 10 shown in FIG. 2 is provided on the substrate 20, and includes a source electrode 30 and a drain electrode 40, an organic semiconductor layer (conductive layer of the present invention) 50, a gate insulating layer 60, and a gate electrode 70. These are stacked in this order from the substrate 20 side.

  Specifically, in the organic TFT 10, the source electrode 30 and the drain electrode 40 are separately provided on the substrate 20, and the organic semiconductor layer 50 is provided so as to cover the electrodes 30 and 40. Further, a gate insulating layer 60 is provided on the organic semiconductor layer 50, and a gate electrode 70 is further provided thereon so as to overlap at least a region between the source electrode 30 and the drain electrode 40.

In the organic TFT 10, a region between the source electrode 30 and the drain electrode 40 in the organic semiconductor layer 50 is a channel region 510 in which carriers move. Hereinafter, in this channel region 510, the length in the direction of carrier movement, that is, the distance between the source electrode 30 and the drain electrode 40 is the channel length L, and the length perpendicular to the channel length L direction is the channel width W. To tell.
Such an organic TFT 10 is an organic TFT having a configuration in which the source electrode 30 and the drain electrode 40 are provided on the substrate 20 side with respect to the gate electrode 70 via the gate insulating layer 60, that is, an organic TFT having a top gate structure. .

Hereinafter, each part which comprises organic TFT10 is demonstrated sequentially.
The substrate 20 supports each layer (each part) constituting the organic TFT 10. As the substrate 20, for example, a substrate similar to the substrate 2 described in the organic EL element 1 described above can be used, and a silicon substrate, a gallium arsenide substrate, or the like can be used.
On the substrate 20, a source electrode 30 and a drain electrode 40 are juxtaposed at a predetermined distance along the channel length L direction.

The constituent material of the source electrode 30 and the drain electrode 40 may be any material as long as it has conductivity. For example, Pd, Pt, Au, W, Ta, Mo, Al, Cr, Ti , Cu or metal materials such as alloys containing them, conductive oxide materials such as ITO, FTO, ATO, SnO ₂ , carbon materials such as carbon black, carbon nanotubes, fullerene, polyacetylene, polypyrrole, PEDOT (poly-ethylenedioxythiophene) And conductive polymer materials such as polythiophene, polyaniline, poly (p-phenylene), poly (p-phenylene vinylene), polyfluorene, polycarbazole, polysilane, or derivatives thereof. Polymer materials are usually chlorinated It is used in a state where it is doped with a polymer such as iron, iodine, strong acid, organic acid, polystyrene sulphonic acid, and imparted with conductivity. Further, one or more of these can be used in combination.

The thickness (average) of the source electrode 30 and the drain electrode 40 is not particularly limited, but is preferably about 30 to 300 nm, and more preferably about 50 to 200 nm.
The distance (separation distance) between the source electrode 30 and the drain electrode 40, that is, the channel length L is preferably about 2 to 30 μm, and more preferably about 2 to 20 μm.
The channel width W is preferably about 0.1 to 5 mm, and more preferably about 0.3 to 3 mm.

An organic semiconductor layer 50 is provided on the substrate 20 so as to cover the source electrode 30 and the drain electrode 40.
As the constituent material of the organic semiconductor layer 50, the conductive material of the present invention can be used.
As described above, the conductive material of the present invention can adjust the characteristics of the carrier transport ability of the polymer to be formed by appropriately selecting the substituent R ¹ .
Therefore, by appropriately selecting the substituent R ¹ , it is possible to impart hole transporting or electron transporting semiconductor characteristics to the polymer, and therefore the conductive material of the present invention is used for the organic semiconductor layer 50. Is particularly effective.

Specifically, if it is assumed the organic TFT10 of p-type, as the material of the organic semiconductor layer 50, since the excellent hole transporting ability is selected, in particular, the formula as a substituent R ¹ (D1), (D4) or (D5) (however, ^{Q 2} is S, O, if the Se or Te) polymer comprising is preferably used. Also, if it is assumed the organic TFT10 of n-type, as the material of the organic semiconductor layer 50, since the excellent electron transporting ability is selected, in particular, the formula as the substituent R ¹ (D2), A polymer having (D6) or (D9) (provided that Q ² is NT ³ or O) is preferably used.

The thickness (average) of the organic semiconductor layer 50 is preferably about 0.1 to 1000 nm, more preferably about 1 to 500 nm, and further preferably about 10 to 100 nm. Thereby, it can prevent that organic TFT10 enlarges (especially that thickness increases), maintaining the outstanding carrier transport capability.
In addition, by using the organic semiconductor layer 50 that is composed mainly of a polymer such as the conductive material of the present invention, the resulting organic TFT 10 can be reduced in thickness and weight, and can be reduced. Excellent flexibility. Such an organic TFT 10 is suitable for application to a switching element of a flexible display including the above-described organic EL element.

Note that the organic semiconductor layer 50 is not limited to a structure provided so as to cover the source electrode 30 and the drain electrode 40, and is provided at least in a region (channel region 510) between the source electrode 30 and the drain electrode 40. It only has to be.
A gate insulating layer 60 is provided on the organic semiconductor layer 50.
The gate insulating layer 60 insulates the gate electrode 70 from the source electrode 30 and the drain electrode 40.

The gate insulating layer 60 is preferably mainly composed of an organic material (particularly an organic polymer material). The gate insulating layer 60 containing an organic polymer material as a main material can be easily formed and can improve the adhesion to the organic semiconductor layer 50.
Examples of such organic polymer materials include polystyrene, polyimide, polyamideimide, polyvinylphenylene, polycarbonate (PC), acrylic resin such as polymethyl methacrylate (PMMA), and polytetrafluoroethylene (PTFE). Fluorine resin, phenolic resin such as polyvinylphenol or novolac resin, and olefinic resins such as polyethylene, polypropylene, polyisobutylene, polybutene, etc. are used, and one or more of these may be used in combination. it can.

  The thickness (average) of the gate insulating layer 60 is not particularly limited, but is preferably about 10 to 5000 nm, and more preferably about 100 to 1000 nm. By setting the thickness of the gate insulating layer 60 within the above range, the organic TFT 10 is increased in size while the source electrode 30 and the drain electrode 40 are reliably insulated from the gate electrode 70 (in particular, the thickness is increased). ) Can be prevented.

Note that the gate insulating layer 60 is not limited to a single-layer structure, and may have a multilayer structure.
A gate electrode 70 is provided on the gate insulating layer 60.
As the constituent material of the gate electrode 70, the same constituent materials as those of the source electrode 30 and the drain electrode 40 described above can be used.

The thickness (average) of the gate electrode 70 is not particularly limited, but is preferably about 0.1 to 5000 nm, more preferably about 1 to 5000 nm, and still more preferably about 10 to 5000 nm.
In the organic TFT 10 as described above, the amount of current flowing between the source electrode 30 and the drain electrode 40 is controlled by changing the voltage applied to the gate electrode 70.

That is, in the OFF state in which no voltage is applied to the gate electrode 70, even if a voltage is applied between the source electrode 30 and the drain electrode 40, almost no carriers are present in the organic semiconductor layer 50, so that a very small current Only flows. On the other hand, in the ON state in which a voltage is applied to the gate electrode 70, charges are induced in the portion of the organic semiconductor layer 50 facing the gate insulating layer 60, and a carrier flow path is formed in the channel region 510. When a voltage is applied between the source electrode 30 and the drain electrode 40 in this state, carriers (holes or electrons) flow through the channel region 510.
Such an organic TFT 10 can be manufactured as follows, for example.
3 to 4 are views (longitudinal sectional views) for explaining a method of manufacturing the organic TFT 10 shown in FIG. In the following description, the upper side in FIGS. 3 to 4 is referred to as “upper” and the lower side is referred to as “lower”.

[B1] Source and drain electrode formation process
[B1-1] First, a substrate 20 as shown in FIG. 3A is prepared, and this substrate 20 is washed with, for example, water (pure water or the like), an organic solvent, or the like alone or in an appropriate combination.
Next, a photoresist is supplied onto the substrate 20 to form a film 80 ′ (see FIG. 3B).

The photoresist supplied onto the substrate 20 is a negative photoresist that is exposed to light (exposure) is cured, and a region other than the exposed region is dissolved and removed by development, and exposed. Any positive type photoresist in which the region is dissolved and removed by development may be used.
Negative photoresists include rosin-dichromate, polyvinyl alcohol (PVA) -bichromate, shellac-bichromate, casein-dichromate, PVA-diazo, acrylic photoresist, etc. And water-soluble photoresists such as oil-soluble photoresists such as polyvinyl cinnamate, cyclized rubber-azide, polyvinyl cinnamylidene acetate, and polycinnamic acid β-vinyloxyethyl ester.

Examples of positive photoresists include oil-soluble photoresists such as o-naphthoquinonediazide.
As a method for supplying the photoresist onto the substrate 20, any method may be used, but a coating method is preferably used.
As a coating method, the same method as described in the hole transport layer forming step [A2] of the method for producing the organic EL element 1 can be used.
Next, the film 80 ′ is exposed and developed through a photomask to form a resist layer 80 having an opening 820 in a region where the source electrode 30 and the drain electrode 40 are to be formed (see FIG. 3C). .

[B1-2] Next, as shown in FIG. 3D, in the opening 820 of the substrate 20 that has been subjected to the processing described above, depending on the source electrode 30 and the drain electrode 40 to be formed, A predetermined amount of the liquid material 90 containing these electrode constituent materials or precursors thereof is supplied.

In this liquid material 90, the solution or dispersion medium for dissolving or dispersing the constituent material of the source electrode 30 and the drain electrode 40 or the precursor thereof is the same as that described in the hole transport layer forming step [A2]. Things can be used.
In addition, as a method for supplying the liquid material 90 into the opening 820, a coating method similar to that described above can be used, but among these, an inkjet method (droplet discharge method) is preferably used. . According to the inkjet method, the liquid material 90 can be discharged as a droplet from the nozzle of the droplet discharge head and reliably supplied into the opening 820. As a result, it is possible to reliably prevent the liquid material 90 from adhering to the resist layer 80.

[B1-3] Next, the solvent or dispersion medium is removed from the liquid material 90 supplied to the opening 820 to form the source electrode 30 and the drain electrode 40.
The temperature at the time of removing the solvent or dispersion medium (removal temperature) is not particularly limited, and is slightly different depending on the type of the solvent or dispersion medium, but is preferably about 20 to 200 ° C, and about 50 to 100 ° C. More preferably. Thereby, the solvent or dispersion medium contained in the liquid material 90 can be reliably removed.
In addition, you may make it heat the removal of this solvent or a dispersion medium under reduced pressure. Thereby, the solvent or the dispersion medium contained in the liquid material 90 can be more reliably removed.

[B1-4] Next, the resist layer 80 is removed from the substrate 20 to obtain the source electrode 30 and the drain electrode 40 formed on the substrate 20 (see FIG. 4F).
The removal method of the resist layer 80 may be appropriately selected according to the type of the resist layer 80. For example, ashing such as plasma treatment or ozone treatment, ultraviolet irradiation, Ne-He laser, Ar laser, CO ₂ laser, It can be carried out by irradiation with various lasers such as ruby laser, semiconductor laser, YAG laser, glass laser, YVO ₄ laser, excimer laser, contact with a solvent capable of dissolving or decomposing the resist layer 80 (for example, immersion).

[B2] Organic Semiconductor Layer Formation Step Next, as shown in FIG. 4 (h), the organic layer is formed on the substrate 20 on which the source electrode 30 and the drain electrode 40 are formed so as to cover the source electrode 30 and the drain electrode 40. A semiconductor layer 50 is formed.
At this time, a channel region 510 is formed between the source electrode 30 and the drain electrode 40 (region corresponding to the gate electrode 70).
This organic semiconductor layer 50 is formed using the composition for conductive material of the present invention by the same method as described in the hole transport layer forming step [A2] of the method for producing the organic EL element 1.

The organic semiconductor layer 50 is composed mainly of the conductive material (polymer) of the present invention. Thereby, in the next step [B3], when the gate insulating layer material is supplied onto the organic semiconductor layer 50, the polymer is preferably swollen and dissolved by the solvent or dispersion medium contained in the gate insulating layer material. Can be suppressed or prevented. As a result, phase dissolution between the organic semiconductor layer 50 and the gate insulating layer 60 can be reliably prevented.
In addition, in the organic TFT 10 obtained by configuring the organic semiconductor layer 50 using a polymer as a main material like the conductive material of the present invention, in the vicinity of the interface between the organic semiconductor layer 50 and the gate insulating layer 60, It is possible to reliably prevent the constituent materials from being mixed with each other over time.

[B3] Gate Insulating Layer Formation Step Next, as shown in FIG. 4I, a gate insulating layer 60 is formed on the organic semiconductor layer 50 by a coating method.
Specifically, the gate insulating layer 60 is formed by applying (supplying) a solution containing an insulating material or a precursor thereof onto the organic semiconductor layer 50 using the application method described above, and then applying the coating as necessary. The film can be formed by post-treatment (for example, heating, infrared irradiation, application of ultrasonic waves, etc.).

[B4] Gate Electrode Formation Step Next, as shown in FIG. 4J, the gate electrode 70 is formed on the gate insulating layer 60 by a coating method.
Specifically, the gate electrode 70 is applied (supplied) on the gate insulating layer 60 using a coating method with a solution containing an electrode material or a precursor thereof, and then applied to the coating film as necessary. The film can be formed by post-treatment (for example, heating, infrared irradiation, application of ultrasonic waves, etc.).

As the coating method, the same method as described above can be used, but it is particularly preferable to use the ink jet method. According to the inkjet method, a solution containing an electrode material or a precursor thereof can be patterned by discharging droplets from a nozzle of a droplet discharge head. As a result, the gate electrode 70 having a predetermined shape can be easily and reliably formed on the gate insulating layer 60.
Through the steps as described above, the organic TFT 10 is manufactured.

<Electronic equipment>
Moreover, the electronic devices of the present invention such as the organic EL element (light emitting element) 1 and the organic TFT (switching element) 10 as described above can be used in various electronic devices.
FIG. 5 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.

In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.
In the personal computer 1100, for example, the display unit 1106 includes the organic EL element (light emitting element) 1 and the organic TFT (switching element) 10 described above.

FIG. 6 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.
In the mobile phone 1200, for example, the display unit includes the organic EL element (light emitting element) 1 and the organic TFT (switching element) 10 described above.

FIG. 7 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.
In the digital still camera 1300, for example, the display unit includes the organic EL element (light emitting element) 1 and the organic TFT (switching element) 10 described above.
A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.

A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the data communication input / output terminal 1314 as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

  In addition to the personal computer (mobile personal computer) of FIG. 5, the mobile phone of FIG. 6, and the digital still camera of FIG. 7, the electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, Monitor direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV Monitors, electronic binoculars, POS terminals, devices with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasound diagnostic devices, internal Endoscope display device), fish finder, various measuring instruments, Vessels such (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector.

As mentioned above, although the composition for electroconductive materials of this invention, an electroconductive material, a conductive layer, an electronic device, and an electronic device were demonstrated based on embodiment of illustration, this invention is not limited to these.
For example, when the conductive layer is used as a hole transport layer, the electronic device of the present invention can be applied to an organic EL element which is an example of the above-described display element (light emitting element), for example, a light receiving element (photoelectric conversion). The present invention can be applied to a solar cell which is an example of an element.

Moreover, when using an electroconductive layer as an organic-semiconductor layer, the electronic device of this invention can be applied to the organic TFT which is an example of the switching element mentioned above, for example, can be applied to a semiconductor element etc.
Furthermore, the conductive layer of the present invention can be applied to, for example, wirings and electrodes in addition to being used as the above-described hole transport layer. In this case, the electronic device of the present invention can be applied to, for example, a wiring board.

Next, specific examples of the present invention will be described.
1. Synthesis of compounds First, compounds (A) to (S) as shown below were prepared.
<Compound (A)>
-1A- First, 6- (p-aminophenyl) hexanol was treated with benzyl bromide and sodium hydride in anhydrous dimethylformamide to convert and protect the hydroxyl group to a benzyl ether group.

-2A- Next, 1 mol of the obtained compound was dissolved in 150 mL of acetic acid, and acetic anhydride was added dropwise at room temperature, followed by stirring. After completion of the reaction, the precipitated solid was filtered, washed with water and dried.
-3A- Next, 0.37 mol of benzyl ether derivative obtained from 6- (p-aminophenyl) hexanol, 0.66 mol of 1-bromonaphthalene, 1.1 mol of potassium carbonate, copper powder and iodine were mixed, And heated. After allowing to cool, 130 mL of isoamyl alcohol, 50 mL of pure water, and 0.73 mol of potassium hydroxide were added and the mixture was stirred and dried.

Further, 130 mmol of the compound obtained there, 62 mmol of 4,4′-diiodobiphenyl, 1.3 mmol of palladium acetate, 5.2 mmol of t-butylphosphine, 260 mmol of t-butoxynatrim, and 700 mL of xylene were mixed. Stir at ° C. Then, it stood to cool and crystallized.
-5A- The obtained compound was reduced with hydrogen gas under a Pd-C catalyst, converted from a benzyl ether group to a hydroxyl group, and deprotected.

-6A- Next, 100 mmol of the compound and 200 mmol of acryloyl chloride were added to a xylene solution, stirred while heating, allowed to cool and crystallized to obtain a compound.
And mass spectrum (MS) method, ¹ H-nuclear magnetic resonance ( ¹ H-NMR) spectrum method, ¹³ C-nuclear magnetic resonance ( ¹³ C-NMR) spectrum method, and Fourier transform infrared absorption (FT-IR) It was confirmed by a spectral method that the obtained compound was the following compound (A).

<Compound (B)>
Compound (B) was obtained in the same manner as Compound (A) except that p- (bromomethyl) styrene was used instead of acryloyl chloride.
<Compound (C)>
The compound (C) was obtained in the same manner as the compound (A) except that the following step -6A'- was used instead of the step -6A-.
-6A'- Next, 100 mmol of the compound was added to a 50% aqueous potassium hydroxide solution and stirred while heating. Next, acetylene was reacted at a flow rate of 1 liter per hour for 10 hours while maintaining at 150 ° C. under pressure (5 MPa), and then allowed to cool and crystallize to obtain a compound.

<Compound (D)>
The compound (D) was obtained in the same manner as the compound (A) except that the following step -6A "-was used instead of the step -6A-.
-6A "-Next, 100 mmol of the compound and 2000 mmol of epichlorohydrin were added to a 50% aqueous sodium hydroxide solution to which a small amount of tetra-n-butylammonium hydrogensulfate (phase transfer catalyst) was added, and the mixture was stirred at room temperature for 10 hours. Thereafter, the mixture was allowed to cool and crystallized to obtain a compound.

<Compound (E)>
Compound (E) was obtained in the same manner as Compound (D) except that 2- (p-aminophenyl) ethanol was used instead of 6- (p-aminophenyl) hexanol.
<Compound (F)>
Compound (F) was obtained in the same manner as Compound (D) except that 8- (p-aminophenyl) octanol was used instead of 6- (p-aminophenyl) hexanol.

<Compound (G)>
Compound (G) was obtained in the same manner as Compound (D) except that 1- (p-aminophenyl) methanol was used instead of 6- (p-aminophenyl) hexanol.
<Compound (H)>
Compound (H) was obtained in the same manner as Compound (D) except that 3,3′-diiodo-1,1′-biisobenzothiophene was used instead of 4,4′-diiodobiphenyl. .

<Compound (I)>
Compound (I) was obtained in the same manner as Compound (D) except that 2,5-bis (4-iodophenyl) -thiophene was used instead of 4,4′-diiodobiphenyl.
<Compound (J)>
Compound (J) was obtained in the same manner as Compound (D) except that 2-bromo-9,9-dioctylfluorene was used instead of 1-bromonaphthalene.

<Compound (K)>
Compound (K) was obtained in the same manner as Compound (D) except that 2-bromothiophene was used instead of 1-bromonaphthalene.
<Compound (L)>
Compound (L) was obtained in the same manner as Compound (D) except that 2-bromo-1,3,4-oxadiazole was used instead of 1-bromonaphthalene.

<Compound (M)>
As the following compound (M), N, N, N ′, N′-tetrakis (4-methylphenyl) -benzidine (manufactured by Tosco Corporation, “OSA6140”) was prepared.
<Compound (N)>
As the following compound (N), poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (manufactured by Bayer, “Vitron P”) was prepared.

<Compound (O)>
As the following compound (O), 3,5-bis (4-tert-butyl-phenyl), 4-phenyl-1,2,4-triazole (manufactured by Tosco Corporation, “OPA2938”) was prepared.
<Compound (P)>
As the following compound (P), poly [(9,9-dioctyl-2,7-divinylenefluorenylene) -ortho-co (9,10-anthracene)] (manufactured by American Dye Source, “ADS106RE”) Prepared.

<Compound (Q)>
Poly [9,9-dioctyl-2,7-divinylenefluorenylene-ortho-co (4,4′-biphenylene)] as the following compound (Q)
(American Dye Source, “ADS107GE”) was prepared.
<Compound (R)>
As the following compound (R), poly [(9,9-dioctylfluorenyl-2,7-diyl) -co (1,4-vinylenephenylene)]
(American Dye Source, “ADS128GE”) was prepared.

<Compound (S)>
As the following compound (S), poly [(9,9-dioctylfluorenyl-2,7-diyl) -co (N, N′-diphenyl) -N, N′-di ((p-butylphenyl)- 1,4-
Diaminobenzene))]] (manufactured by American Dye Source, “ADS132GE”) was prepared.

2. Manufacture of an organic EL element Five organic EL elements were manufactured in each of the following Examples and Comparative Examples.
Example 1A
[Preparation of hole transport material]
Using the compound (A) as the arylamine derivative, the compound (A) and a radical polymerization initiator (“Irgacure 651” manufactured by Nagase Sangyo Co., Ltd.) are dissolved in xylene at a weight ratio of 95: 5 to form holes. A transport material (composition for conductive material) was obtained.

[Production of organic EL element]
-1B- First, an ITO electrode (anode) having an average thickness of 100 nm was formed on a transparent glass substrate having an average thickness of 0.5 mm by vacuum deposition.
-2B- Next, the hole transport material was applied onto the ITO electrode by a spin coating method and dried.
Thereafter, the compound (A) is irradiated with ultraviolet rays having a wavelength of 185 nm and an irradiation intensity of 3 mW / cm ^{2 in} the atmosphere for 400 seconds using a filter in a mercury lamp (USHIO, “UM-452 model”). A hole transport layer having an average thickness of 50 nm was formed by polymerization reaction.

-3B- Next, a 1.5 wt% xylene solution of the compound (P) (light emitting material) was applied on the hole transport layer by a spin coating method, and then dried to form a light emitting layer having an average thickness of 50 nm. Formed.
-4B- Next, the compound (O) was vacuum-deposited on the light-emitting layer to form an electron transport layer having an average thickness of 20 nm.
-5B- Next, an AlLi electrode (cathode) having an average thickness of 300 nm was formed on the electron transport layer by vacuum deposition.
-6B- Next, a protective cover made of polycarbonate was placed so as to cover each formed layer, and fixed and sealed with an ultraviolet curable resin to complete an organic EL element.
(Example 2A)
An organic EL device was manufactured after preparing a hole transporting material in the same manner as in Example 1A except that the compound (B) was used as the arylamine derivative.

(Example 3A)
[Preparation of hole transport material]
Using compound (C) as an arylamine derivative, compound (C) and a photocationic polymerization initiator (manufactured by Sumitomo 3M, "FC-508") are dissolved in xylene at a weight ratio of 99: 1, A hole transport material (composition for conductive material) was obtained.

[Production of organic EL element]
-1C- In the same manner as in Step -1B-, an ITO electrode (anode) having an average thickness of 100 nm was formed on a transparent glass substrate having an average thickness of 0.5 mm.
-2C- Next, the hole transport material was applied onto the ITO electrode by a spin coat method and dried.
Then, using a filter for a mercury lamp (USHIO, “UM-452 model”), irradiated with ultraviolet rays having a wavelength of 365 nm and an irradiation intensity of 500 mW / cm ^{2 in} a dry atmosphere for 15 seconds and then heated at 110 ° C. for 60 minutes Thus, the compound (A) was polymerized to form a hole transport layer having an average thickness of 50 nm.

-3C- In the same manner as in Step -3B-, a light emitting layer having an average thickness of 50 nm, in which the compound (P) was formed as a light emitting material, was formed on the hole transport layer.
-4C- In the same manner as in Step -4B-, an electron transport layer having an average thickness of 20 nm composed of the compound (O) as a main material was formed on the light emitting layer.
-5C- In the same manner as in Step 5B-, an AlLi electrode (cathode) having an average thickness of 300 nm was formed on the electron transport layer.
-6C- In the same manner as in Step 6B-, the organic EL element was completed by sealing with a polycarbonate protective cover.

(Examples 4A to 6A)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3A, except that the arylamine derivative shown in Table 1 was used.
(Examples 7A to 14A)
A hole transport material was prepared in the same manner as in Example 3A except that the arylamine derivative and the light emitting material shown in Table 1 were used, and then an organic EL device was produced.

(Comparative Example 1A)
[Preparation of hole transport material]
Compound (M) was dissolved in xylene to obtain a hole transport material.
[Production of organic EL element]
An organic EL device was produced in the same manner as in Example 1A except that, in the step-2A-, the irradiation of ultraviolet rays by a mercury lamp was omitted.

(Comparative Example 2A)
[Preparation of hole transport material]
A 2.0 wt% aqueous dispersion was prepared by dispersing the compound (N) in water to obtain a hole transport material.
In addition, as a compound (N), the ratio of 3, 4- ethylenedioxythiophene and a styrenesulfonic acid used 1:20 by weight ratio.
[Production of organic EL element]
An organic EL device was produced in the same manner as in Comparative Example 1A except that the hole transport material prepared here was used as the hole transport material.

(Comparative Example 3A)
[Preparation of hole transport material]
Using the compound (M) as the arylamine derivative derivative and the polyester acrylate compound (“Aronix M-8030” manufactured by Toagosei Co., Ltd.) as the photocrosslinking agent, the compound (M), the polyester acrylate compound, the radical polymerization initiator ( Nagase Sangyo Co., Ltd. product: Irgacure 651) was mixed with xylene at a weight ratio of 30: 65: 5 to obtain a hole transport material.
[Production of organic EL element]
An organic EL device was produced in the same manner as in Example 1A except that the hole transport material prepared here was used as the hole transport material.
(Comparative Example 4A)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3A except that the compound (G) was used as the arylamine derivative.

3. Evaluation of organic EL elements For the organic EL elements of the examples and comparative examples, the light emission luminance (cd / m ² ) and the maximum light emission efficiency (lm / W) were measured, respectively, and the light emission luminance was reduced to half of the initial value. The time (half-life) was measured.
Each measured value was determined from five organic EL elements.

The measurement of light emission luminance was performed by applying a voltage of 6 V between the ITO electrode and the AlLi electrode.
Then, each measurement value measured in each Example and each Comparative Example is set to the following four levels using each measurement value (luminescence brightness, maximum luminous efficiency, half-life) measured in Comparative Example 1A as a reference value. Evaluation was performed according to the criteria.

A: The measurement value of Comparative Example 1A is 1.50 times or more. O: The measurement value of Comparative Example 1A is 1.25 times or more and less than 1.50 times. Δ: The measurement value of Comparative Example 1A. In contrast, 1.00 times or more and less than 1.25 times x: 0.75 times or more and less than 1.00 times the measured value of Comparative Example 1A. Table 1 shows.

As shown in Table 1, all the organic EL elements of each example had excellent results in terms of light emission luminance, maximum light emission efficiency, and half-life as compared with the organic EL elements of each comparative example.
Thereby, it became clear that the interaction between main skeletons was suitably reduced in the organic EL element of the present invention. Moreover, it became clear that the phase dissolution of the hole transport layer and the light emitting layer was suitably prevented.

Further, by appropriately selecting the substituent X, in each example, the more the main skeleton separation distance is kept at an appropriate size, the better the emission luminance, the maximum emission efficiency, and the half-life A result indicating an extension of was obtained.
Furthermore, also in Examples 9A to 14A, results were obtained in which the formed organic EL elements exhibited excellent emission luminance, maximum emission efficiency, and half-life. This is because, by appropriately selecting the substituent R ¹ of the compound (A1), the characteristics of the carrier transport ability of the conductive material are changed, and the combination with the light emitting material is suitable. I guessed that.

4). Production of Organic TFT Five organic TFTs were produced in each of the following Examples and Comparative Examples.
(Example 1B)
[Preparation of organic semiconductor materials]
An organic semiconductor material (composition for conductive material) was obtained in the same manner as in the hole transport material of Example 3A, except that the compound (D) was used as the arylamine derivative.

[Manufacture of organic TFT]
-1E- First, a glass substrate having an average thickness of 1 mm was prepared and washed with water (cleaning liquid).
Next, a photoresist was applied on a glass substrate by a spin coating method, and then a pre-baking process was performed to form a film.
Next, the coating film was developed after being irradiated (exposed) with ultraviolet rays through a photomask. Thus, a resist layer having an opening in a region where the source electrode and the drain electrode are formed was formed.

-2E- Next, a gold colloid aqueous solution was supplied into the opening by an inkjet method. Thereafter, the glass substrate supplied with the aqueous gold colloid solution was dried by heating to obtain a source electrode and a drain electrode.
-3E- Next, after removing the resist layer by oxygen plasma treatment, the glass substrate on which the source electrode and the drain electrode were formed was sequentially washed with water and methanol.

-4E- Next, except that the organic semiconductor material prepared here was used instead of the hole transport material, the compound (D) was subjected to a polymerization reaction in the same manner as in Step-2C- An organic semiconductor layer having a thickness of 50 nm was formed.
-5E- Next, a butyl acetate solution of polymethyl methacrylate (PMMA) was applied on the organic semiconductor layer by a spin coat method, and then dried to form a gate insulating layer having an average thickness of 500 nm.
-6E- Next, an aqueous dispersion of polyethylene dioxythiophene was applied to the portion corresponding to the region between the source electrode and the drain electrode on the gate insulating layer by an ink jet method and then dried. Thereby, a gate electrode having an average thickness of 100 nm was formed.
The organic TFT was manufactured by the above process.
(Examples 2B-8B)
An organic TFT was manufactured after preparing an organic semiconductor material in the same manner as in Example 1B, except that the arylamine derivatives used in the organic semiconductor material were those shown in Table 2.

(Comparative Example 1B)
[Preparation of organic semiconductor materials]
Compound (M) was dissolved in xylene to obtain an organic semiconductor material.
[Production of organic TFT]
An organic TFT was produced in the same manner as in Example 1B, except that in the step 4E-, the irradiation with ultraviolet rays by the mercury lamp and the heat treatment were omitted.

(Comparative Example 2B)
[Preparation of organic semiconductor materials]
Using compound (M) as the arylamine derivative and using a bifunctional epoxy compound (manufactured by Nagase ChemteX Corporation, “Denacol EX-212”) as a photocrosslinking agent, compound (M), an epoxy compound, and a cationic photopolymerization initiator (Sumitomo 3M, “FC-508”) was mixed with xylene at a weight ratio of 50: 49: 1 to obtain an organic semiconductor material.
[Production of organic TFT]
An organic TFT was manufactured in the same manner as in Example 1B except that the organic semiconductor material prepared here was used as the organic semiconductor material.
(Comparative Example 3B)
An organic TFT was manufactured after preparing an organic semiconductor material in the same manner as in Example 1B except that the compound (G) was used as the arylamine derivative used for the organic semiconductor material.

5). Evaluation of Organic TFT The values of OFF current and ON current were measured for the organic TFTs produced in each Example and each Comparative Example.
Here, the OFF current is a value of a current that flows between the source electrode and the drain electrode when no gate voltage is applied, and the ON current is the value of the source electrode when the gate voltage is applied. It is the value of the current flowing between the drain electrode.

Therefore, the larger the ratio of the absolute value of the OFF current and the absolute value of the ON current (ON / OFF ratio), the more the organic TFT has better characteristics.
The OFF current was measured with the potential difference between the source electrode and the drain electrode as 30 V, and the ON current was measured with the potential difference between the source electrode and the drain electrode as 30 V and the absolute value of the gate voltage as 40 V.
And the value of ON / OFF ratio measured by each Example and each comparative example was evaluated in accordance with the following four steps, respectively.

A: ON / OFF ratio value is 10 ⁴ or more B: ON / OFF ratio value is 10 ³ or more, less than 10 ⁴ Δ: ON / OFF ratio value is 10 ² or more, 10 ³ × less than: the value of the oN / OFF ratio is less than 10 ² these evaluation results, respectively, shown in Table 2 below.

As shown in Table 2, each of the organic TFTs of each example had a large ON / OFF ratio value and excellent characteristics as compared with the organic TFT of each comparative example.
Thereby, it became clear that the interaction between the main skeletons was suitably reduced. Moreover, it became clear that the phase dissolution of the organic semiconductor layer and the gate insulating layer was suitably prevented.
In addition, by appropriately selecting the substituent X, in each example, as the main skeleton separation distance is maintained at an appropriate size, the value of the ON / OFF ratio is larger and the result shows better characteristics. was gotten.

It is the longitudinal cross-sectional view which showed an example of the organic EL element. It is a figure which shows embodiment of organic TFT, (a) is a longitudinal cross-sectional view, (b) is a top view. It is a figure (longitudinal sectional drawing) for demonstrating the manufacturing method of the organic TFT shown in FIG. It is a figure (longitudinal sectional drawing) for demonstrating the manufacturing method of the organic TFT shown in FIG. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Organic EL element 2 ... Substrate 3 ... Anode 4 ... Organic EL layer 41 ... Hole transport layer 42 ... Light emitting layer 43 ... Electron transport layer 5 ... Cathode 6 ... Protective layer 10 ... Organic thin film transistor 20 ... Substrate 30 ... Source electrode 40 ... Drain electrode 50 ... Organic semiconductor layer 510 ... Channel region 60 ... Gate insulating layer 70 ... Gate electrode 80 ... Resist layer 80 '... Coating 820 ... ... Opening 90 ... Liquid material 1100 ... Personal computer 1102 ... Keyboard 1104 ... Main body 1106 ... Display unit 1200 ... Mobile phone 1202 ... Operation buttons 1204 ... Earpiece 1206 ... Speaker 1300 ... ... Digital still camera 1302 ... Case (body) 1304 ... Light receiving unit 1306 ... ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... Input / output terminal for data communication 1430 ... Television monitor 1440 ... Personal computer

Claims (22)

The composition for electroconductive materials characterized by containing the compound represented by the following general formula (A1).

[Wherein, two Xs represent any of substituents represented by the following general formulas (B1) to (B4). However, the two Xs may have the same or different carbon number. Two R ^{1 s} each independently represent a substituted or unsubstituted monovalent aromatic group (excluding a phenyl group). Four R < ² > represents a hydrogen atom, a methyl group, or an ethyl group each independently. Y represents a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) which are substituted or unsubstituted. ]

[In these formulas, n ¹ represents an integer of ² to 8, n ² represents an integer of ³ to 8, and n ³ represents an integer of ³ to 8. m ¹ represents an integer of 0 to 3, and m ² represents an integer of 0 to 2. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

[In these formulas, n ⁴ represents an integer of 1 to 3. ]   The composition for conductive materials according to claim 1, wherein the two substituents X have the same carbon number.   The composition for conductive materials according to claim 1 or 2, wherein the substituent X is bonded to any of the 3-position, 4-position, and 5-position of the benzene ring. The composition for conductive materials according to claim ¹ , wherein the two substituents R ¹ are the same. The composition for a conductive material according to claim ¹ , wherein the total number of carbon atoms of the substituent R ¹ is 2 to 30. The composition for a conductive material according to claim 1, wherein the substituent R ¹ is a monocyclic or condensed polycyclic aromatic group. A conductive material obtained by polymerizing a compound represented by the following general formula (A1) in the substituent X.

[Wherein, two Xs represent any of substituents represented by the following general formulas (B1) to (B4). However, the two Xs may have the same or different carbon number. Two R ^{1 s} each independently represent a substituted or unsubstituted monovalent aromatic group (excluding a phenyl group). Four R < ² > represents a hydrogen atom, a methyl group, or an ethyl group each independently. Y represents a divalent aromatic group represented by any one of the following general formulas (C1) to (C3) which are substituted or unsubstituted. ]

[In these formulas, n ¹ represents an integer of ² to 8, n ² represents an integer of ³ to 8, and n ³ represents an integer of ³ to 8. m ¹ represents an integer of 0 to 3, and m ² represents an integer of 0 to 2. Z ¹ represents a hydrogen atom or a methyl group, and Z ² represents a hydrogen atom, a methyl group or an ethyl group. ]

[In these formulas, n ⁴ represents an integer of 1 to 3. ]   The conductive material according to claim 7, wherein the compound undergoes a polymerization reaction by light irradiation.   A conductive layer formed using the composition for conductive material according to claim 1.   A conductive layer comprising the conductive material according to claim 7 or 8 as a main material.   The conductive layer according to claim 9, wherein the conductive layer is a hole transport layer.   The conductive layer according to claim 11, wherein the hole transport layer has an average thickness of 10 to 150 nm.   The conductive layer according to claim 9, wherein the conductive layer is an organic semiconductor layer.   The conductive layer according to claim 13, wherein an average thickness of the organic semiconductor layer is 0.1 to 1000 nm.   An electronic device comprising the conductive layer according to claim 9.   An electronic device comprising the laminate having the conductive layer according to claim 11.   The electronic device according to claim 16, wherein the electronic device is a light emitting element or a photoelectric conversion element.   The electronic device according to claim 17, wherein the light emitting element is an organic electroluminescence element.   An electronic device comprising a laminate having the conductive layer according to claim 13.   The electronic device according to claim 19, wherein the electronic device is a switching element.   21. The electronic device according to claim 20, wherein the switching element is an organic thin film transistor.   An electronic apparatus comprising the electronic device according to any one of claims 15 to 21.

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