JP4311336B2 - Composition for conductive material, conductive material, conductive layer, electronic device and electronic apparatus - Google Patents

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 degradation of properties such as poor luminous efficiency, color purity or color accuracy as an 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.

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、Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４は、それぞれ独立して、下記一般式（２）で表される置換基を表し、同一であっても、異なっていてもよく、８つのＲ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し、同一であっても、異なっていてもよく、Ｙは、置換もしくは無置換の芳香族炭化水素環を少なくとも１つ含む基を表す。］

［式中、ｎは、３〜８の整数を表し、ｍは、０〜３の整数を表し、Ｚ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し、同一であっても、異なっていてもよい。］
これにより、キャリア輸送能の優れた導電層を形成することができる導電性材料用組成物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 (1).

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a substituent represented by the following general formula (2), and may be the same or different; Each R independently represents a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring; Represents a group. ]

[In the formula, n represents an integer of 3 to 8, m represents an integer of 0 to 3, and Z each independently represents a hydrogen atom, a methyl group or an ethyl group, , May be different. ]
Thereby, it can be set as the composition for conductive materials which can form the conductive layer excellent in carrier transport ability.

In the composition for conductive material of the present invention, the substituent X ¹ and the substituent X ³ are preferably the same.
Thereby, in the polymer (conductive material) obtained by polymerizing the compounds represented by the general formula (1) in any of the substituents X ¹ , X ² , X ³ and X ⁴ , The interaction between main skeletons other than the substituents X ¹ , X ² , X ³ and X ^{4 of the} compound represented by the general formula (1) can be suitably prevented. As a result, the carrier transport ability of the polymer can be improved.

In the composition for conductive material of the present invention, the substituent X ² and the substituent X ⁴ are preferably the same.
Thereby, in the polymer obtained, the interaction between the main skeletons can be suitably prevented. As a result, the carrier transport ability of the polymer can be improved.
In the composition for conductive material of the present invention, the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are preferably the same.
Thereby, in the polymer obtained, the interaction between the main skeletons can be more suitably prevented. As a result, the carrier transport ability of the polymer can be particularly improved.

In the composition for a conductive material of the present invention, the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are each in the 3rd, 4th or 5th position of the benzene ring to which they are bonded. It is preferably bound to any of the positions.
Thereby, in the obtained polymer, the adjacent main skeletons can be more reliably separated from each other, and the main skeletons can be more reliably prevented from being too close to each other.

In the composition for conductive material of the present invention, the group Y is preferably composed of a carbon atom and a hydrogen atom.
Thereby, the carrier transport ability of the polymer becomes excellent, and the formed conductive layer becomes more excellent in carrier transport ability.
In the composition for conductive material of the present invention, the total number of carbon atoms of the group Y is preferably 6-30.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.

In the composition for conductive material of the present invention, in the group Y, the number of the aromatic hydrocarbon rings is preferably 1 to 5.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.
In the composition for a conductive material of the present invention, the group Y is preferably a biphenylene group or a derivative thereof.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.

［式中、Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４は、それぞれ独立して、下記一般式（２）で表される置換基を表し、同一であっても、異なっていてもよく、８つのＲ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し、同一であっても、異なっていてもよく、Ｙは、置換もしくは無置換の芳香族炭化水素環を少なくとも１つ含む基を表す。］

［式中、ｎは、３〜８の整数を表し、ｍは、０〜３の整数を表し、Ｚ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し、同一であっても、異なっていてもよい。］
これにより、キャリア輸送能の優れた導電性材料とすることができる。 The conductive material of the present invention is obtained by subjecting compounds represented by the following general formula (1) to a polymerization reaction in any ^{one of} the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ^4. It is characterized by that.

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a substituent represented by the following general formula (2), and may be the same or different; Each R independently represents a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring; Represents a group. ]

[In the formula, n represents an integer of 3 to 8, m represents an integer of 0 to 3, and Z each independently represents a hydrogen atom, a methyl group or an ethyl group, , May be different. ]
Thereby, it can be set as the electroconductive material excellent in carrier transport ability.

In the conductive material of the present invention, it is preferable that the substituent X ¹ and the substituent X ³ are the same.
Thereby, interaction between main skeletons can be prevented suitably. As a result, the carrier transport ability of the polymer (conductive material) can be improved.

In the conductive material of the present invention, the substituent X ² and the substituent X ⁴ are preferably the same.
Thereby, interaction between main skeletons can be prevented suitably. As a result, the carrier transport ability of the polymer (conductive material) can be improved.
In the conductive material of the present invention, it is preferable that the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are the same.
Thereby, interaction between main skeletons can be prevented more suitably. As a result, the carrier transport ability of the polymer (conductive material) can be particularly improved.

In the conductive material of the present invention, the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are each selected from the 3-position, 4-position or 5-position of the benzene ring to which they are bonded. It is preferable that it has couple | bonded with either.
Thereby, the adjacent main skeletons can be more reliably separated from each other, and the main skeletons can be more reliably prevented from being too close to each other.

In the conductive material of the present invention, the group Y is preferably composed of a carbon atom and a hydrogen atom.
Thereby, the carrier transport ability of the polymer (conductive material) becomes excellent, and the formed conductive layer becomes more excellent in carrier transport ability.
In the conductive material of the present invention, the total number of carbon atoms of the group Y is preferably 6-30.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.

In the conductive material of the present invention, in the group Y, the number of the aromatic hydrocarbon rings is preferably 1 to 5.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.
In the conductive material of the present invention, the group Y is preferably a biphenylene group or a derivative thereof.
Thereby, the carrier transport ability of the polymer is further improved, and the formed conductive layer is particularly excellent in the carrier transport ability.

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 to be polymerized.
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, an organic EL element with high luminous efficiency 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.
An electronic apparatus according to the present invention includes the electronic device according to the present invention.
As a result, 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.
<Organic electroluminescence device>
First, 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”) 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.
Between the anode 3 and the cathode 5, an organic EL layer 4 is provided. 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 (conductive layer of the present invention) 41 has a function of transporting holes injected from the anode 3 to the light emitting layer 42.
The hole transport layer 41 is composed mainly of the conductive material of the present invention.

The conductive material of the present invention includes compounds (diphenylamine derivatives) represented by the following general formula (1), each having substituents X ¹ , X ² , X ³ and X ⁴ (hereinafter collectively referred to as these). Or a “substituent X”)), and a polymer (polymer) obtained by a polymerization reaction as a main component.

［式中、Ｘ^１、Ｘ^２、Ｘ^３およびＸ^４は、それぞれ独立して、下記一般式（２）で表される置換基を表し、同一であっても、異なっていてもよく、８つのＲ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し、同一であっても、異なっていてもよく、Ｙは、置換もしくは無置換の芳香族炭化水素環を少なくとも１つ含む基を表す。］

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a substituent represented by the following general formula (2), and may be the same or different; Each R independently represents a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring; Represents a group. ]

［式中、ｎは、３〜８の整数を表し、ｍは、０〜３の整数を表し、Ｚ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し、同一であっても、異なっていてもよい。］

[In the formula, n represents an integer of 3 to 8, m represents an integer of 0 to 3, and Z each independently represents a hydrogen atom, a methyl group or an ethyl group, , May be different. ]

In such a polymer, main skeletons (diphenylamine skeletons) other than the substituent X are linked to each other by a chemical structure generated by a reaction in the substituent X (hereinafter, this chemical structure is referred to as “linked structure”). This facilitates the formation of a two-dimensional network.
The main skeleton has a conjugated chemical structure, and contributes to smooth hole transport in the polymer due to its unique electron cloud spread.

In particular, in the polymer of the present invention, the main skeletons are separated from each other by a predetermined distance via a connecting structure, so that the interaction between adjacent main skeletons is reduced, and the hole between them is reduced. Delivery will be carried out smoothly.
In the polymer of the present invention, the main skeleton is connected so as to form a network. For example, even if there is a portion where the bond is broken in a part of the network, it passes through another route. Holes will be transported smoothly.

Furthermore, since the polymer in the present invention is likely to form a network having a two-dimensional (planar) spread, it is possible to effectively prevent or suppress the occurrence of entanglement between the polymers. Also from the viewpoint, the hole can be transported smoothly.
Such a polymer as the main component of the conductive material of the present invention has a structure as described above, that is, the main skeletons are separated from each other by a predetermined distance via a connecting structure, and a network is easily formed. By these synergistic effects, extremely excellent hole transport ability (carrier transport ability) is exhibited. As a result, the hole transport layer 41 mainly composed of the conductive material of the present invention has a particularly excellent hole transport capability.

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 becomes difficult to transfer holes between them, and the hole transport ability of the polymer tends to decrease.
From this viewpoint, the structure of the substituent X, that is, the general formula (2) may be set.

  Therefore, the substituent X is composed of a linear carbon-carbon bond in which n is 3 to 8 and m is 0 to 3 in the above general formula (2), and particularly n is 4 to 6 and m is preferably composed of a linear carbon-carbon bond having 1 or 2. This makes it 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 holes are transferred between the main skeletons. Therefore, the hole transport ability of the polymer is excellent.

The total number of n and m in the substituent X ¹ and the substituent X ³ is preferably substantially the same, and more preferably the same. Thus, it is possible to reduce variations in the distance between the main skeletons linked by polymerization reaction of the substituents X (the substituent X ¹ or a substituent X ^3). That is, the variation in the separation distance between the main skeletons in the polymer can be reduced. As a result, it is possible to preferably prevent the electron density from being biased in the polymer. Thereby, the hole transport ability of the polymer can be improved.
From this viewpoint, the total number of n and m in the substituent X ² and the substituent X ⁴ is also preferably substantially the same, and more preferably the same. Thereby, the said effect improves more and can improve the hole transport ability of a polymer | macromolecule more.

Furthermore, the above-mentioned effect can be obtained by making the total number of n and m in the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ almost the same, more preferably the same. Is particularly prominent. In addition, since the lengths of the substituents X protruding from the main skeleton are almost the same (particularly the same), the possibility of steric hindrance due to the substituents X can be reduced. Thereby, the polymerization reaction between the substituents X can be reliably performed. That is, the polymer can be reliably formed. As a result, the hole transport ability of the polymer can be further improved.

By the way, as shown in the general formula (2), the substituent X has a styrene derivative group in which a substituent Z is introduced into the styrene group as a functional group at the end thereof. A benzene ring will be present.
Since this benzene ring also has a conjugated chemical structure, if the benzene ring and the main skeleton having a conjugated chemical structure are too close, for example, the benzene ring and the main skeleton are bonded by an ether bond. If the total number of n and m is 2, or the like, the adjacent main skeletons interact with each other through this benzene ring.

  However, in the conductive material of the present invention, the bond between the main skeleton and the benzene ring is formed through a total number of n and m of 3 or more, that is, 3 or more methylene groups and an ether bond. . Thereby, the separation 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 is a hydrogen atom, a methyl group or an ethyl group, but the substituent Z may be selected according to the total number of n and m, that is, the total number of methylene groups.
For example, when the total number is small, the substituent Z may be a methyl group or an ethyl group. Here, since the methyl group and the ethyl group are electron-donating substituents, by selecting a methyl group and an ethyl group as the substituent Z, electrons can be biased toward the main skeleton. As a result, it is possible to suitably prevent the adjacent main skeletons from interacting with each other via the benzene ring.

From the above, the two substituents X (substituent X ¹ and substituent X ³ , or substituent X ¹ and substituent X ³ ) are preferably substantially the same, more preferably the same. preferable. As a result, the three-dimensional structures of these substituents X are substantially equal to each other, and the effects as described above are more remarkably exhibited. As a result, it is possible to more suitably suppress or prevent the main skeletons from interacting with each other, thereby further improving the hole transport ability of the polymer.
Further, the four substituents X are preferably substantially the same, and more preferably the same. As a result, the effects as described above are more remarkably exhibited, and the hole transport ability of the polymer can be particularly improved.

In addition, since the styrene derivative group has high reactivity, the substituent X can be polymerized relatively easily to form a polymer having a long chain length.
Furthermore, the styrene derivative group is a product other than the product obtained by combining these when the substituents X undergo a polymerization reaction, that is, when the styrene derivative groups are combined (bonded). Since it is difficult to generate a product, impurities can be suitably prevented from being mixed into the conductive material.
The substituent X may be bonded to any position from the 2-position to the 6-position of the benzene ring, but is particularly preferably bonded to any one of the 3-position, 4-position or 5-position. . Thereby, the effect of performing the coupling | bonding of adjacent main frame | skeletons via a connection structure can be exhibited more notably. That is, the adjacent main skeletons can be separated more reliably.

Next, the main skeleton contributing to hole transport in the polymer will be described.
The substituent R is a hydrogen atom, a methyl group or an ethyl group, and the substituent R may be selected according to the number of carbon atoms of the substituent X. For example, when the carbon number of the substituent X is large, a hydrogen atom is selected as the substituent R, and when the carbon number of the substituent X is small, the substituent R is a methyl group or an ethyl group. You may make it choose.

The group (bonding group) Y may be any group as long as it contains at least one substituted or unsubstituted aromatic hydrocarbon ring. In particular, a group composed of a carbon atom and a hydrogen atom is preferable. Thereby, the hole transport ability of the polymer becomes excellent, and the formed hole transport layer 41 becomes more excellent in hole transport ability.
Specifically, examples of the structure including at least one aromatic hydrocarbon ring include those represented by the following chemical formulas (3) to (19).

Further, the total number of carbon atoms of the group Y is preferably 6-30, more preferably 10-25, and even more preferably 10-20.
Further, in the group Y, the number of aromatic hydrocarbon rings is preferably 1 to 5, more preferably 2 to 5, and even more preferably 2 or 3.
Considering these, in the compound represented by the general formula (1), as the group Y, a biphenylene group or a derivative thereof is a particularly preferable structure.
Thereby, the hole transport ability (carrier transport ability) of the polymer becomes more excellent, and the formed hole transport layer 41 has particularly excellent hole transport ability.

In addition, in the group Y, when a substituent is introduced into the aromatic hydrocarbon ring, the substituent is not particularly limited as long as the planarity of the group Y can be maintained. A linear alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
Further, the hole transport layer 41 is composed of a polymer having a network shape that has undergone a polymerization reaction, like the conductive material of the present invention, so that the durability of the hole transport layer 41, that is, the solvent resistance. Can be improved. As a result, when forming the light emitting layer 42 on the hole transport layer 41 in step [3] to be described later, the conductive material is swollen by the solvent or dispersion medium contained in the material for forming the light emitting layer 42. Alternatively, dissolution can be suppressed or prevented.

Furthermore, the conductive material of the present invention is mainly composed of a polymer obtained by reacting (bonding) a styrene derivative group of the substituent X between the compounds represented by the general formula (1). is there.
Here, since the bond between styrene derivative groups exhibits excellent bond stability, the conductive material (polymer) of the present invention exhibits excellent water resistance and chemical resistance.
By these things, phase dissolution with the positive hole transport layer 41 and the light emitting layer 42 can be prevented reliably.
Further, such a conductive material 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.
Further, 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.
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 energization (voltage is applied) between the anode 3 and the cathode 5, holes move in the hole transport layer 41 and electrons move in the electron transport layer 43. Will 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 luminescent materials include various low-molecular luminescent materials and various high-molecular luminescent materials as described below, and at least one of them 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, coronene 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), Various metal complexes such as (2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine) platinum (II) can be mentioned.

  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.

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.
In the present embodiment, the light emitting layer 42 is provided separately from the hole transport layer 41 and the electron transport layer 43, but the hole transporting light emitting layer serving as the hole transport layer 41 and the light emitting layer 42 is used. Alternatively, an electron-transporting light-emitting layer that also serves as the electron-transporting 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 42, respectively.

In addition, 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.
In addition, an arbitrary target layer may be provided between the layers 3, 4, and 5. For example, a hole injection layer can be provided between the hole transport layer 41 and the anode 3, and an electron injection layer or the like can be provided between the electron transport layer 43 and the cathode 5. Thus, when providing a positive hole injection layer in the organic EL element 1, the electroconductive material of this invention can also be used for this positive hole injection layer. Moreover, when providing an electron injection layer in the organic EL element 1, an alkali halide such as LiF can be used for the electron injection layer in addition to the electron transport material as described above.

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.

[1] 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.

[2] Hole transport layer forming step [2-1] First, a composition for a conductive material (hole transport material) containing the compound represented by the general formula (1) is applied (supplied) onto the anode 3. )
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 represented by the general formula (1) is dissolved in a solvent or dispersed in a dispersion medium, examples of the solvent or dispersion medium used include nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, and four. Inorganic solvents such as carbon chloride and ethylene carbonate, ketone solvents such as methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, methanol, ethanol, isopropanol, ethylene glycol , Alcohol solvents such as diethylene glycol (DEG) and glycerin, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), aniso , Ether solvents such as diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cellosolv solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane , Aromatic hydrocarbon solvents such as toluene, xylene and benzene, aromatic heterocyclic compounds solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, N, N-dimethylformamide (DMF), N, N Amide solvents such as dimethylacetamide (DMA), halogen compound solvents such as dichloromethane, chloroform, 1,2-dichloroethane, ester solvents such as ethyl acetate, methyl acetate, ethyl formate, dimethylsulfoxide Various organic solvents such as sulfur compound solvents such as DMSO, sulfolane, nitrile solvents such as acetonitrile, propionitrile, acrylonitrile, organic acid solvents such as formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, or And mixed solvents containing these.

In addition, it is preferable to add a polymerization initiator to the composition for conductive materials. Thereby, in the next step [2-2], the polymerization reaction in the substituent X can be promoted when performing a predetermined treatment such as heating or light irradiation.
The polymerization initiator is not particularly limited, and examples thereof include a photopolymerization initiator such as a photocationic polymerization initiator and a radical photopolymerization initiator, a thermal polymerization initiator, an anaerobic polymerization initiator, and the like. It is particularly preferable to use a photo radical polymerization initiator. Thereby, in the next step [2-2], the substituent X can be polymerized relatively easily.

As the radical photopolymerization initiator, various radical photopolymerization initiators can be used. For example, benzophenone, benzoin, acetophenone, benziketal, Michler's ketone, acylphosphine oxide, ketocoumarin, xanthene and Photo radical polymerization initiators such as thioxanthone can be used.
Furthermore, when using a photoinitiator as a polymerization initiator, you may add the sensitizer suitable for a photoinitiator to the composition for electroconductive materials.

[2-2] Next, the hole transport material supplied on the anode 3 is irradiated with light.
As a result, a polymer having a network shape (conductive material of the present invention) in which the compounds represented by the general formula (1) contained in the hole transport material are polymerized in the substituent X is generated. A hole transport layer 41 (conducting layer of the present invention) mainly composed of molecules 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 [3], the hole transport layer 41 is highly concentrated by the solvent or dispersion medium contained in the light emitting layer material. Swelling and dissolution of molecules can be suppressed or prevented. As a result, phase dissolution of the hole transport layer 41 and the light emitting layer 42 can be reliably prevented.

The weight average molecular weight of the polymer is not particularly limited, but is preferably about 1,000 to 1,000,000, and more preferably about 10,000 to 300,000. Thereby, swelling and dissolution of the polymer can be suppressed or prevented more reliably.
In addition, the hole transport layer 41 contains a low molecule (monomer or oligomer) of the compound represented by the general formula (1) within a range in which the phase dissolution of the hole transport layer 41 and the light emitting layer 42 is prevented. May be included.

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.
The wavelength of the ultraviolet rays to be irradiated is preferably about 100 to 420 nm, and more preferably about 150 to 400 nm.

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.
By setting the ultraviolet wavelength, irradiation intensity, and irradiation time within such ranges, the progress of the polymerization reaction of the hole transport material supplied onto the anode 3 can be controlled relatively easily.

The predetermined treatment for causing the polymerization reaction in the substituent X includes, for example, heating and anaerobic treatment in addition to the light irradiation as described above, and 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 to be polymerized.
Further, the obtained hole transport layer 41 may be subjected to a heat treatment, for example, in the air, in an inert atmosphere, under reduced pressure (or in a vacuum) or the like, if necessary. Thereby, for example, the coating film can be dried (desolvent or dedispersing medium), solidified, and the like. In addition, you may dry a coating film irrespective of heat processing.

[3] 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.

[4] Electron Transport Layer Formation Step Next, the electron transport layer 43 is formed on the light emitting layer 42.
The electron transport layer 43 can be formed in the same manner as the light emitting layer 42. That is, the electron transport layer 43 can be formed by the method described with respect to the light emitting layer 42 using the electron transport material as described above.

[5] 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.

[6] Protection Layer Formation Step Next, the protection 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.

<Electronic equipment>
Moreover, the organic EL element (electronic device of the present invention) 1 of the present invention can be used for various electronic devices.
FIG. 2 is a perspective view showing the 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 (electronic device) 1 described above.

FIG. 3 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 (electronic device) 1 described above.

FIG. 4 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 (electronic device) 1 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 input / output terminal 1314 for data communication 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.

  The electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, in addition to the personal computer (mobile personal computer) in FIG. 2, the mobile phone in FIG. 3, and the digital still camera in FIG. 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 equipped with touch panels (for example, cash dispensers and automatic ticket vending machines for financial institutions), 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 conductive materials, the conductive material, the conductive layer, the electronic device, and the electronic apparatus of the present invention have been described based on the illustrated embodiments, the present invention is not limited thereto. .
For example, 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) when the conductive layer is used as a hole transport layer, 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.
Furthermore, the conductive layer of the present invention can be applied to, for example, a wiring, an electrode, an organic semiconductor layer and the like in addition to being used as the hole transport layer described above. In this case, the electronic device of the present invention can be applied to, for example, a switching element (thin film transistor), a wiring board, a semiconductor element, and the like.

Next, specific examples of the present invention will be described.
1. Synthesis of compounds First, compounds (A) to (K) as shown below were prepared.
<Compound (A)>
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.

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.
Next, a dried product (benzyl ether derivative) obtained by converting hydroxyl group to benzyl ether group from 6- (p-bromophenyl) hexanol by the same treatment as that applied to 6- (p-aminophenyl) hexanol. )

  Next, 0.37 mol of benzyl ether derivative obtained from 6- (p-aminophenyl) hexanol, 0.66 mol of benzyl ether derivative obtained from 6- (p-bromophenyl) hexanol, 1.1 mol of potassium carbonate, copper Powder and iodine were mixed and heated at 200 ° C. After standing 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 and stirred at 120 ° C. did. Then, it stood to cool and crystallized.
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.

Next, 100 mmol of this compound and 200 mmol of p- (bromomethyl) styrene were added to a xylene solution, stirred for 10 hours while heating, then 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 4,4′-diiodo-2,2′-dimethylbiphenyl was used in place of 4,4′-diiodobiphenyl.

<Compound (C)>
Compound (C) was obtained in the same manner as Compound (A) except that 2′-bromo-4-ethylstyrene was used instead of p- (bromomethyl) styrene.

<Compound (D)>
Except for using 2- (p-aminophenyl) propanol in place of 6- (p-aminophenyl) hexanol and using 2- (p-bromophenyl) propanol in place of 6- (p-bromophenyl) hexanol. In the same manner as in the compound (A), a compound (D) was obtained.

<Compound (E)>
Compound (E) is the same as Compound (D) except that 2- (2 ′, 6′-dimethyl-4′-aminophenyl) propanol is used instead of 2- (p-aminophenyl) propanol. Got.

<Compound (F)>
Compound (F) was obtained in the same manner as Compound (D) except that 3′-bromo-4-propylstyrene was used instead of p- (bromomethyl) styrene.

<Compound (G)>
Except for using 8- (p-aminophenyl) octanol instead of 6- (p-aminophenyl) hexanol and using 8- (p-bromophenyl) octanol instead of 6- (p-bromophenyl) hexanol. In the same manner as in the compound (A), a compound (G) was obtained.

<Compound (H)>
Compound (H) was obtained in the same manner as Compound (A) except that 8- (p-aminophenyl) octanol was used instead of 6- (p-aminophenyl) hexanol.

<Compound (I)>
1- (p-aminophenyl) methanol was used instead of 6- (p-aminophenyl) hexanol, and 1- (p-bromophenyl) methanol was used instead of 6- (p-bromophenyl) hexanol. The compound (I) was obtained in the same manner as the compound (A).

<Compound (J)>
As the following compound (H), N, N, N ′, N′-tetrakis (4-methylphenyl) -benzidine (“OSA6140” manufactured by Tosco Corporation) was prepared.

<Compound (K)>
As the following compound (I), poly (3,4-ethylenedioxythiophene / styrene sulfonic acid) (manufactured by Bayer, “Vitron P”) was prepared.

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

[Production of organic EL element]
-1- 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.
-2- 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 on a mercury lamp (USHIO, “UM-452 model”). Crosslinking was performed to form a hole transport layer having an average thickness of 50 nm.

-3- Next, on the hole transport layer, poly (9,9-dioctyl-2,7-divinylenefluorenyl-ortho-co (anthracene-9,10-diyl) (weight average molecular weight 200000) A 1.7 wt% xylene solution was applied by spin coating and then dried to form a light emitting layer having an average thickness of 50 nm.
-4- Next, 3,4,5-triphenyl-1,2,4-triazole was vacuum deposited on the light emitting layer to form an electron transport layer having an average thickness of 20 nm.
−5- Next, an AlLi electrode (cathode) having an average thickness of 300 nm was formed on the electron transport layer by vacuum deposition.
-6 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 2)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the compound (B) was used as the diphenylamine derivative.
(Example 3)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the compound (C) was used as the diphenylamine derivative.

(Example 4)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the compound (D) was used as the diphenylamine derivative.
(Example 5)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the compound (E) was used as the diphenylamine derivative.

(Example 6)
An organic EL device was produced after preparing a hole transport material in the same manner as in Example 1 except that the compound (F) was used as the diphenylamine derivative.
(Example 7)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the compound (G) was used as the diphenylamine derivative.
(Example 8)
An organic EL device was manufactured after preparing a hole transporting material in the same manner as in Example 1 except that the compound (H) was used as the diphenylamine derivative.

(Comparative Example 1)
[Preparation of hole transport material]
Compound (J) was dissolved in dichloroethane to obtain a hole transport material.
[Production of organic EL element]
An organic EL device was manufactured in the same manner as in Example 1 except that the irradiation of ultraviolet rays with a mercury lamp was omitted in Step -2-.

(Comparative Example 2)
[Preparation of hole transport material]
A 2.0 wt% aqueous dispersion was prepared by dispersing the compound (K) in water to obtain a hole transport material.
In addition, as the compound (K), a compound having a ratio of 3,4-ethylenedioxythiophene and styrenesulfonic acid of 1:20 by weight was used.

[Production of organic EL element]
An organic EL device was produced in the same manner as in Comparative Example 1 except that the hole transport material was used as the hole transport material.
(Comparative Example 3)
[Preparation of hole transport material]
Using compound (J) as the diphenylamine derivative, using polyester acrylate compound (“Aronix M-8030” manufactured by Toagosei Co., Ltd.) as the photocrosslinking agent, compound (J), polyester acrylate compound, photo radical polymerization initiator (Nagase) “Irgacure 651” manufactured by Sangyo Co., Ltd. was mixed with dichloroethane 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 1 except that the hole transport material was used as the hole transport material.
(Comparative Example 4)
An organic EL device was manufactured after purifying the hole transport material in the same manner as in Example 1 except that the compound (I) was used as the diphenylamine derivative.

2. Evaluation For each of the organic EL elements of the examples and comparative examples, the emission luminance (cd / m ² ) and the maximum emission efficiency (lm / W) were measured, and the time during which the emission luminance was half the initial value (halved) Period).
Moreover, each measured value calculated | required the average value of 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, with each measurement value (emission luminance, maximum luminous efficiency, half-life) measured in Comparative Example 1 as a reference value, each measurement value measured in each Example and each Comparative Example is divided into the following four stages. Evaluation was performed according to the criteria.

A: The measurement value of Comparative Example 1 is 1.50 times or more. O: The measurement value of Comparative Example 1 is 1.25 times or more and less than 1.50 times. Δ: The measurement value of Comparative Example 1 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 with respect to the measured value of Comparative Example 1 Table 1 shows.

As shown in Table 1, each of the organic EL elements of the examples (organic EL elements including a hole transport layer mainly composed of the conductive material of the present invention) is compared with the organic EL elements of the comparative examples. Thus, excellent results were obtained in terms of emission luminance, maximum emission efficiency, and half-life.
Thereby, in the organic EL device of the present invention, it has been clarified that the interaction between the main skeletons is preferably reduced and the phase dissolution between the hole transport layer and the light emitting layer is preferably 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.

It is the longitudinal cross-sectional view which showed an example of the organic EL element. 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 1100 ... Personal computer 1102 ... Keyboard 1104 ... Main body 1106 ... Display unit 1200 ... Mobile phone 1202 ... Operation buttons 1204 ... Earpiece 1206 ... Mouthpiece 1300 ... Digital still camera 1302 ... Case (body) 1304 ... Light receiving unit 1306 ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... I / O terminal for data communication 1430 ... Television monitor 1440 ... Personal computer

Claims (19)

The composition for electroconductive materials characterized by containing the compound represented by following General formula (1).

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a substituent represented by the following general formula (2), and may be the same or different; Each R independently represents a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring; Represents a group. ]

[In the formula, n represents an integer of 3 to 8, m represents an integer of 0 to 3, and Z each independently represents a hydrogen atom, a methyl group or an ethyl group, , May be different. ] The composition for a conductive material according to claim ¹ , wherein the substituent X ¹ and the substituent X ³ are the same. Wherein the substituents X ² and the substituent X ⁴ are conductive material composition according to claim 1 or 2 are identical. The composition for conductive materials according to claim ¹ , wherein the substituent X ¹ , the substituent X ² , the substituent X ^3, and the substituent X ⁴ are the same. The substituent X ¹ , the substituent X ² , the substituent X ^3, and the substituent X ⁴ are bonded to any one of the 3-position, 4-position, and 5-position of the benzene ring to which they are bonded. The composition for conductive materials according to any one of claims 1 to 4.   The said group Y is a composition for electroconductive materials in any one of Claim 1 thru | or 5 comprised by the carbon atom and the hydrogen atom.   The composition for a conductive material according to any one of claims 1 to 6, wherein the total number of carbon atoms of the group Y is 6 to 30.   In the said group Y, the number of the said aromatic hydrocarbon rings is 1-5, The composition for conductive materials in any one of Claim 1 thru | or 7.   The composition for a conductive material according to claim 1, wherein the group Y is a biphenylene group or a derivative thereof. A conductive material obtained by subjecting compounds represented by the following general formula (1) to a polymerization reaction in any of substituent X ¹ , substituent X ² , substituent X ³ and substituent X ⁴ .

[Wherein, X ¹ , X ² , X ³ and X ⁴ each independently represent a substituent represented by the following general formula (2), and may be the same or different; Each R independently represents a hydrogen atom, a methyl group or an ethyl group, and may be the same or different, and Y contains at least one substituted or unsubstituted aromatic hydrocarbon ring; Represents a group. ]

[In the formula, n represents an integer of 3 to 8, m represents an integer of 0 to 3, and Z each independently represents a hydrogen atom, a methyl group or an ethyl group, , May be different. ]   The conductive compound according to claim 10, 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 10 as a main material.   The conductive layer according to claim 12 or 13, wherein the conductive layer is a hole transport layer.   The conductive layer according to claim 14, wherein the hole transport layer has an average thickness of 10 to 150 nm.   An electronic device comprising a laminate having the conductive layer according to claim 12.   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 apparatus comprising the electronic device according to claim 16.

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