JP2006140287A - Composition for conductive material, conductive material, conductive layer, electronic device and electronic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a conductive material capable of forming a conductive layer excellent in carrier transportability, the conductive material using the composition, and an electronic device and an apparatus principally comprising the conductive material. <P>SOLUTION: The composition for the conductive material contains a compound represented by a general formula (1), and an urethane (meta)acrylate based cross-linking agent. In the formula, X<SP>1</SP>-X<SP>4</SP>represent substituents represented by H<SB>2</SB>C=CZ-COO-(CH<SB>2</SB>)<SB>n</SB>-, and eight R represent hydrogen, methyl or ethyl groups, and Y represents a group including an aromatic hydrocarbon ring. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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.

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、２〜８の整数を表し、Ｚは、水素原子またはメチル基を表す。］
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) and a urethane (meth) acrylate-based crosslinking agent.

[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. ]

[Wherein, n represents an integer of 2 to 8, and Z represents a hydrogen atom or a methyl group. ]
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 materials of the present invention, the urethane (meth) acrylate crosslinking agent includes an aromatic urethane (meth) acrylate crosslinking agent, an alicyclic urethane (meth) acrylate crosslinking agent, and an aliphatic urethane (meta It is preferable that the main component is at least one of acrylate-based crosslinking agents.
Thereby, the substituents X ¹ , X ² , X ³ and X ⁴ between the compounds represented by the general formula (1) (hereinafter, these may be collectively referred to as “substituent X”). High flexibility, toughness, and chemical resistance are imparted to a polymer (conductive material) obtained by polymerization reaction of any of these directly or via a urethane (meth) acrylate crosslinking agent can do.

In the composition for conductive material of the present invention, the urethane (meth) acrylate-based crosslinking agent preferably has at least two (meth) acryloyl groups.
Thereby, in the obtained polymer, the substituents X can be more reliably connected to each other via the urethane (meth) acrylate-based crosslinking agent, and adjacent main skeletons are kept at a more appropriate distance. be able to.

［式中、ｎは、１〜１００の整数を表し、２つの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、異なっていてもよく、２つの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。］
これにより、主骨格同士の離間距離を適切なものに保つことができる。その結果、形成される高分子は、正孔輸送能がより優れたものとなる。 In the composition for conductive material of the present invention, the urethane (meth) acrylate-based cross-linking agent is preferably composed mainly of a compound represented by the following general formula (3).

[Wherein, n represents an integer of 1 to 100, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different, and may represent two A ^2. Each independently represents a group obtained by removing two isocyanate groups from a diisocyanate compound and may be the same or different. ]
Thereby, the separation distance between main skeletons can be kept appropriate. As a result, the formed polymer has a more excellent hole transport capability.

［式中、ｎは、１〜９０の整数を表し、２つの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。］
これにより、形成される高分子は、比較的高い湿度の雰囲気中においても、変質、劣化し難いものとなる。 In the composition for conductive material of the present invention, the urethane (meth) acrylate-based cross-linking agent is preferably composed mainly of a compound represented by the following general formula (4).

[Wherein, n represents an integer of 1 to 90, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different. ]
Thereby, the formed polymer is hardly deteriorated or deteriorated even in an atmosphere of relatively high humidity.

In the composition for conductive material of the present invention, the substituent X ¹ and the substituent X ³ are preferably the same.
Thereby, the electric influence with respect to the main frame | skeleton by the substituent X varies, and it can prevent or suppress that the bias | inclination of an electron density arises in a polymer | macromolecule due to this. 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, it is possible to more suitably prevent or suppress the occurrence of uneven electron density in the polymer. As a result, the carrier transport ability of the polymer can be further 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, it is possible to more suitably prevent or suppress the occurrence of uneven electron density in the polymer. As a result, the carrier transport ability of the polymer can be further 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、２〜８の整数を表し、Ｚは、水素原子またはメチル基を表す。］
これにより、優れたキャリア輸送能を有する導電性材料（高分子）とすることができる。 The conductive material of the present invention can be produced by directly or directly forming a substituent X ¹ , a substituent X ² , a substituent X ³ and a substituent X ⁴ between the compounds represented by the following general formula (1) or urethane ( It is obtained by polymerizing via a (meth) acrylate-based crosslinking agent.

[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. ]

[Wherein, n represents an integer of 2 to 8, and Z represents a hydrogen atom or a methyl group. ]
Thereby, it can be set as the electroconductive material (polymer) which has the outstanding carrier transport ability.

In the conductive material of the present invention, the urethane (meth) acrylate-based crosslinking agent includes an aromatic urethane (meth) acrylate-based crosslinking agent, an alicyclic urethane (meth) acrylate-based crosslinking agent, and an aliphatic urethane (meth) acrylate-based. It is preferable that the main component is at least one of the crosslinking agents.
Thereby, excellent flexibility, toughness, and chemical resistance can be imparted to the polymer.

In the conductive material of the present invention, it is preferable that the urethane (meth) acrylate-based crosslinking agent has at least two (meth) acryloyl groups.
Thereby, in the obtained polymer, the substituents X can be reliably connected to each other via the urethane (meth) acrylate-based crosslinking agent, and the adjacent main skeletons are kept at a more appropriate distance. Can do.

［式中、ｎは、１〜１００の整数を表し、２つの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、異なっていてもよく、２つの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。］
これにより、主骨格同士の離間距離を適切なものに保つことができる。その結果、得られた高分子は、正孔輸送能がより優れたものとなる。 In the conductive material of the present invention, it is preferable that the urethane (meth) acrylate-based cross-linking agent contains a compound represented by the following general formula (3) as a main component.

[Wherein, n represents an integer of 1 to 100, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different, and may represent two A ^2. Each independently represents a group obtained by removing two isocyanate groups from a diisocyanate compound and may be the same or different. ]
Thereby, the separation distance between main skeletons can be kept appropriate. As a result, the obtained polymer has a more excellent hole transport ability.

［式中、ｎは、１〜９０の整数を表し、２つの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。］
これにより、得られた高分子は、比較的高い湿度の雰囲気中においても、変質、劣化し難いものとなる。 In the conductive material of the present invention, it is preferable that the aromatic urethane (meth) acrylate-based cross-linking agent has a compound represented by the following general formula (4) as a main component.

[Wherein, n represents an integer of 1 to 90, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different. ]
As a result, the obtained polymer is hardly deteriorated or deteriorated even in a relatively high humidity atmosphere.

In the conductive material of the present invention, the substituent X ¹ and the substituent X ³ are preferably the same.
Thereby, the electric influence with respect to the main frame | skeleton by the substituent X varies, and it can prevent or suppress that the bias | inclination of an electron density arises in a polymer | macromolecule due to this. As a result, the carrier transport ability of the polymer 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, it is possible to more suitably prevent or suppress the occurrence of uneven electron density in the polymer. As a result, the carrier transport ability of the polymer can be further 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 preferably the same.
Thereby, it is possible to more suitably prevent or suppress the occurrence of uneven electron density in the polymer. As a result, the carrier transport ability of the polymer can be further improved.

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, in the polymer, 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 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 and the urethane (meth) acrylate-based crosslinking agent preferably undergo 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.

The conductive layer of the present invention 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.
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.
<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). The main component is a polymer (polymer) obtained by polymerization reaction directly or via a urethane (meth) acrylate-based crosslinking agent. Is.

[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. ]

[Wherein, n represents an integer of 2 to 8, and Z represents a hydrogen atom or a methyl group. ]
In such a polymer, main skeletons (diphenylamine skeletons) other than the substituent X are substituted by a chemical structure formed by a direct reaction between the substituent X and the substituent X, or a urethane (meth) acrylate crosslinking agent. They are linked by a chemical structure formed by crosslinking the group X and the substituent X (hereinafter, these chemical structures are collectively referred to as “linked structure”), thereby making it easier to form a two-dimensional network.

Here, 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 a 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 connection 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.
Considering these things, the structure of the connection structure is selected (determined), that is, the structure (structure) of the substituent X and the urethane (meth) acrylate-based crosslinking agent is set (determined).

  In the connection structure, even when the substituents X are directly polymerized, the interaction between the main skeletons can be reduced. However, the substituent X and the substituent X are urethane (meth) acrylate-based. When the polymerization reaction is performed via the crosslinking agent, the separation distance between the main skeletons is maintained at a more appropriate size, and the interaction between the main skeletons is further reduced. As a result, the polymer having such a connection structure exhibits excellent hole transport ability.

  Substituent X is preferably a linear carbon-carbon bond (alkylene group) in which n is 2 to 8, particularly 2 to 6, in general formula (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.

In addition, the substituent X ¹ and the substituent X ³ preferably have substantially the same carbon number, and more preferably have the same carbon number. As a result, the electrical influence on the main skeleton by the substituent X (substituent X ¹ or substituent X ³ ) varies, and this can suitably prevent or suppress the occurrence of uneven electron density in the polymer. . Thereby, the hole transport ability of the polymer can be improved.
From this viewpoint, it is preferable that the substituent X ² and the substituent X ⁴ have substantially the same carbon number, and more preferably have the same carbon number. Thereby, the said effect improves more and can improve the hole transport ability of a polymer | macromolecule more.

Furthermore, when the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ are preferably substantially the same carbon number, more preferably the same carbon number, the above-described effect is particularly achieved. Prominently demonstrated. Regardless of whether the linking structure is formed by directly bonding substituents X to each other or bonded via a urethane (meth) acrylate-based crosslinking agent, the main skeletons in the polymer are separated from each other. The distance can be made a certain size or more, and the interaction between the main skeletons can be more preferably prevented. As a result, the hole transport ability of the polymer can be further improved.

  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 more reliably separated at an appropriate distance.

  Further, as shown in the general formula (2), the substituent X has a (meth) acryloyl group (when the substituent Z is a hydrogen atom in the general formula (2), an acryloyl group at the terminal. And when the substituent Z is a methyl group, it represents a methacryloyl group. Here, since the (meth) acryloyl group has high reactivity and bond stability, the substituents X are relatively easily polymerized directly or via a urethane (meth) acrylate-based crosslinking agent. Thus, a network having a large two-dimensional spread can be formed.

Furthermore, a double bond (π bond) between an oxygen atom and a carbon atom exists in the linked structure generated by the polymerization reaction using the (meth) acryloyl group. As a result, even when the distance between the main skeletons is relatively long, it is possible to reliably transfer holes between the main skeletons through the π bond.
In addition, since a linear carbon-carbon bond (alkylene group) exists between the π bond and the main skeleton, enhancement of the interaction between the main skeletons can be prevented.

For example, when a structure having many conjugated bonds among π bonds, such as a benzene ring, is present in the chemical structure of the substituent X, when such substituents X are directly bonded, Adjacent main skeletons interact with each other through the structure, and the effect of separating the main skeletons is offset.
On the other hand, the urethane (meth) acrylate-based crosslinking agent used in the present invention is not particularly limited. For example, aromatic urethane (meth) acrylate-based crosslinking agent, alicyclic urethane (meth) acrylate-based crosslinking agent, aliphatic Urethane (meth) acrylate-based cross-linking agents and other various types can be mentioned, and one or more of these can be used in combination.

  Among these, the urethane (meth) acrylate crosslinking agent is an aromatic urethane (meth) acrylate crosslinking agent, an alicyclic urethane (meth) acrylate crosslinking agent, or an aliphatic urethane (meth) acrylate crosslinking agent. What has at least 1 sort (s) as a main component is preferable. These materials are readily available at low cost, and can be synthesized relatively easily. For this reason, the manufacturing cost of the composition for conductive materials can be reduced by using the urethane (meth) acrylate-based crosslinking agent as described above.

  Moreover, these urethane (meth) acrylate type crosslinking agents have excellent flexibility, toughness, and chemical resistance as their characteristics. Therefore, the connection structure obtained by polymerizing the substituents X with each other via the urethane (meth) acrylate crosslinking agent exhibits characteristics derived from the urethane (meth) acrylate crosslinking agent. Thereby, excellent flexibility, toughness, and chemical resistance can be imparted to the conductive material (polymer) of the present invention and the hole transport layer 41 containing the polymer as a main material. As a result, the characteristics of the obtained organic EL element 1 can be improved.

Moreover, since these things show high solubility with respect to various solvents, there is also an advantage that the range of selection of the solvent used for dissolving the composition for conductive material of the present invention is widened.
Furthermore, since these have high transparency, high transparency can be imparted to the formed polymer. Therefore, it is particularly effective to apply the conductive material (polymer) of the present invention to a hole transport layer of an organic EL element that requires transparency.

  In addition, since the (meth) acryloyl group has stable photopolymerization reaction characteristics, it reacts efficiently with the substituent X, and the unreacted substituent X and the urethane (meth) acrylate-based crosslinking agent remain. Can be suitably prevented. As a result, a polymer is formed in which the portion where the substituents X are directly bonded to each other and the portion bonded via the urethane (meth) acrylate-based cross-linking agent are present unevenly (distributed). The hole transport layer 41 having uniform film characteristics can be formed.

Moreover, as such a urethane (meth) acrylate type cross-linking agent, it is not particularly limited as long as it can link the substituent X and the substituent X through this, but at least two (meth) Those having an acryloyl group are preferred. As a result, the substituent X and the substituent X can be more reliably connected via the urethane (meth) acrylate-based crosslinking agent, and when the polymer is formed, the adjacent main skeletons can be connected to each other. A more appropriate distance can be maintained.
As such a urethane (meth) acrylate-based crosslinking agent having at least two (meth) acryloyl groups, various compounds can be used. In particular, a compound represented by the following general formula (3) is a main component. Are preferred.

[Wherein, n represents an integer of 1 to 100, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different, and may represent two A ^2. Each independently represents a group obtained by removing two isocyanate groups from a diisocyanate compound and may be the same or different. ]
What is represented by the general formula (3) is a (meth) acryloyl group at both ends thereof (in the general formula (3), when the substituent A ¹ is a hydrogen atom, it represents an acryloyl group, When the group Z is a methyl group, it represents a methacryloyl group.), And therefore, the polymerization reaction (bonding) with the substituent X can be carried out at both ends thereof.

In addition, since there is a structure linked via urethane bonds between the (meth) acryloyl groups, the length (size) of the structure, that is, two types of A ² and the number of n By appropriately setting, the length (chain length) of the connecting structure can be adjusted. Thereby, the separation distance between main skeletons can be kept appropriate. As a result, the formed polymer has a more excellent hole transport capability.

Further, in those represented by the general formula (3), appropriately selecting the kind of A ^2, i.e. it is sufficient to appropriately select the type of diisocyanate compound. Thereby, when using an aromatic diisocyanate compound as a diisocyanate compound, what is represented by the said General formula (3) can be used as an aromatic urethane (meth) acrylate type crosslinking agent. Moreover, when using an alicyclic diisocyanate compound as a diisocyanate compound, what is represented by the said General formula (3) can be used as an alicyclic urethane (meth) acrylate type crosslinking agent. Furthermore, when using an aliphatic diisocyanate compound as a diisocyanate compound, what is represented by the said General formula (3) can be used as an aliphatic urethane (meth) acrylate type crosslinking agent.

  Specific examples of the aromatic diisocyanate compound include, for example, tolylene-2,4-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, tolylene-2,5-diisocyanate, and tolylene-3,5. -Tolylene diisocyanate (TDI) such as diisocyanate, tolylene-α, 4-diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), p-phenylene Diisocyanate, 1,3-bis- (isocyanatomethyl) -benzene (XDI), m-tetramethylxylene diisocyanate (m-TMXDI), p-tetramethylxylene diisocyanate (p-TMXDI) Una tetramethyl xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate and 4,4'-methylenebis (phenyl isocyanate) and the like.

  Specific examples of the alicyclic diisocyanate compound include, for example, trans-1,4-cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis- (isocyanatomethyl). ) -Cyclohexane (H6XDI) and 3-isocyanatomethyl-3,5,5'-trimethylcyclohexyl isocyanate (IPDI).

Furthermore, examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate (HDI), dimer acid diisocyanate (DDI), and norbornene diisocyanate (NBDI).
Among these, what is represented by the general formula (3) is a compound using tolylene diisocyanate (TDI) as a diisocyanate compound, that is, a compound represented by the following general formula (4) as a main component. Those that do are preferred.

［式中、ｎは、１〜９０の整数を表し、２つの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 represents an integer of 1 to 90, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different. ]

  Here, the benzene ring constituting the compound represented by the general formula (4) has an electron-donating methyl group as a substituent. As a result, the electron density is biased toward the urethane bond side, and the urethane bond is prevented from being attacked by a compound (nucleophilic reagent) having an unshared electron pair such as, for example, water molecule, alcohol and ammonia, or Can be reduced. For this reason, it becomes difficult to generate | occur | produce the cutting | disconnection in a urethane bond, and the polymer (electroconductive material) formed using the urethane (meth) acrylate type crosslinking agent represented by the said General formula (4) has a comparatively high humidity. Even in the atmosphere, it becomes difficult to deteriorate or deteriorate. As a result, the hole transport layer 41 mainly composed of the conductive material of the present invention is excellent in durability.

  Moreover, in what is represented by the said General formula (4), it is preferable that n is an integer of 1-90 as mentioned above. By setting n within the above range, the distance between the main skeletons can be made appropriate. Thereby, in the polymer, the interaction between the adjacent main skeletons can be surely reduced, and the transfer of holes between the main skeletons is reliably performed. As a result, the formed polymer is more excellent in hole transport ability (carrier transport ability).

In addition, although the aromatic urethane (meth) acrylate type crosslinking agent has a benzene ring having a conjugated bond in its chemical structure, for example, a non-conjugated system such as a methylene group or a C—CH ₃ bond. The existence of this chemical structure makes this non-conjugated chemical structure predominate over the benzene ring structure, and suitably prevents or suppresses the interaction of the main skeletons via the benzene ring. can do.

Next, the main skeleton contributing to hole transport in the polymer will be described.
In the compound represented by the general formula (1), 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 (5) to (21).

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 of the polymer becomes more excellent, and the formed hole transport layer 41 has particularly excellent hole transport ability (carrier 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. Thereby, the phase dissolution of the hole transport layer 41 and the light emitting layer 42 can be reliably prevented.
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. Moreover, 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, 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), 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) containing the compound represented by the general formula (1) and a urethane (meth) acrylate-based crosslinking agent. Material) is applied (supplied) onto the anode 3.
In the composition for conductive materials, the compounding ratio of the compound represented by the general formula (1) and the urethane (meth) acrylate-based crosslinking agent is 1: 9 to 9: 1 in terms of molar ratio. Preferably, the ratio is 1: 4 to 4: 1. If the blending ratio of the urethane (meth) acrylate-based crosslinking agent is too small, the main skeletons may not be maintained at a more appropriate distance in the produced polymer, and the main skeletons may interact with each other. When the compounding ratio of the urethane (meth) acrylate crosslinking agent is too large, the mixing ratio of the compound represented by the general formula (1) is relatively reduced. That is, in the polymer to be produced, the abundance ratio of the main skeleton is reduced, so that the hole transport ability may be lowered.

  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), cellosolve 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.
As a result, in the next step [2-2], when a predetermined treatment such as heating or light irradiation is performed, the polymerization reaction between the substituents X or the urethane (meth) acrylate crosslinking agent is promoted. Can be made.
The polymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as photo radical polymerization initiators and photo cationic polymerization initiators, thermal polymerization initiators and anaerobic polymerization initiators, among these, It is particularly preferable to use a photo radical polymerization initiator. Thereby, in the next step [2-2], the polymerization reaction can be relatively easily performed between the substituents X or via the urethane (meth) acrylate-based crosslinking agent.

As the photoradical polymerization initiator, various photoradical polymerization initiators can be used. In addition, photo radical polymerization initiators such as thioxanthone can be used.
Furthermore, when using a photoinitiator as a polymerization initiator, you may make it add the sensitizer suitable for the kind of photoinitiator to be used to the composition for electroconductive materials.

[2-2] Next, the hole transport material supplied on the anode 3 is irradiated with light.
Thereby, the substituent X of the compounds represented by the general formula (1) contained in the hole transport material was polymerized (bonded) directly or via a urethane (meth) acrylate-based crosslinking agent. A network-shaped polymer (conductive material of the present invention) is produced. 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 [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.
The hole transport layer 41 is composed of the compound represented by the general formula (1) or the urethane (meth) acrylate crosslinking agent within a range in which the phase dissolution of the hole transport layer 41 and the light emitting layer 42 is prevented. It may contain a low molecule (monomer or oligomer).

  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 between the substituents X or the urethane (meth) acrylate-based crosslinking agent 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.
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 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.
In addition to the light irradiation, the predetermined treatment for the polymerization reaction between the substituents X or the urethane (meth) acrylate crosslinking agent includes, for example, 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 to be polymerized.

[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, video phone, 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 (I) 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 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 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 the compound and 400 mmol of acryloyl chloride were added to a xylene solution, stirred while heating, and then allowed to cool and crystallize 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)>
Except for using 2- (p-aminophenyl) ethanol instead of 6- (p-aminophenyl) hexanol and using 2- (p-bromophenyl) ethanol instead of 6- (p-bromophenyl) hexanol. In the same manner as in the compound (A), a compound (C) was obtained.

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

<Compound (E)>
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. The compound (E) was obtained in the same manner as the compound (A).

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

<Compound (G)>
Similar to compound (A) except that 4-aminobenzyl alcohol was used instead of 6- (p-aminophenyl) hexanol and (p-bromophenyl) methanol was used instead of (p-aminophenyl) methanol. Thus, a compound (G) was obtained.

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

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

2. Manufacture of Organic EL Element Five organic EL elements were manufactured in each of the following Examples, Reference Examples and Comparative Examples.
Example 1
[Preparation of hole transport material]
Compound (A) as a diphenylamine derivative, urethane acrylate compound (n = 20-30, two A ¹ are hydrogen atoms) represented by the general formula (4) as a urethane (meth) acrylate-based crosslinking agent, light A radical polymerization initiator (“Irgacure 651” manufactured by Nagase Sangyo Co., Ltd.) was used as a polymerization initiator, and these were dissolved in dichloroethane to prepare a hole transport material (composition for conductive material).
The mixing ratio of the compound (A) and the urethane acrylate compound is 17: 2 in terms of molar ratio, and the ratio (weight ratio) between the total weight of the compound (A) and the urethane acrylate compound and the weight of the radical polymerization initiator is set. 19: 1.

[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 ² mW / cm ^{2 in} the atmosphere for 300 seconds using a filter in a mercury lamp (USHIO INC., “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 mixing ratio of the compound (A) and the urethane acrylate compound was 1: 1 in the molar ratio. .
(Example 3)
A hole transport material was prepared in the same manner as in Example 1 except that the molar ratio of the compound (A) and the urethane acrylate compound was 2:17, and then an organic EL device was produced. .

Example 4
The urethane acrylate compound represented by the general formula (4) is the same as in Example 1 except that n is 60 to 70 and two A ¹ are hydrogen atoms. After the preparation, an organic EL device was manufactured.
(Example 5)
The urethane acrylate compound represented by the general formula (4) is the same as in Example 1 except that n is 120 to 140 and two A ¹ are hydrogen atoms. After the preparation, an organic EL device was manufactured.

(Example 6)
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 7)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 2 except that the compound (B) was used as the diphenylamine derivative.

(Example 8)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3 except that the compound (B) was used as the diphenylamine derivative.
Example 9
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 10)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 2 except that the compound (C) was used as the diphenylamine derivative.
(Example 11)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3 except that the compound (C) was used as the diphenylamine derivative.

(Example 12)
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 13)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 2 except that the compound (D) was used as the diphenylamine derivative.

(Example 14)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3 except that the compound (D) was used as the diphenylamine derivative.
(Example 15)
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 16)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 2 except that the compound (E) was used as the diphenylamine derivative.
(Example 17)
An organic EL device was manufactured after preparing the hole transport material in the same manner as in Example 3 except that the compound (E) was used as the diphenylamine derivative.

(Example 18)
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 19)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 2 except that the compound (F) was used as the diphenylamine derivative.

(Example 20)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 3 except that the compound (F) was used as the diphenylamine derivative.
(Reference Example 1)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Example 1 except that the addition of the urethane acrylate compound was omitted.

(Reference Example 2)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (B) was used as the diphenylamine derivative.
(Reference Example 3)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (C) was used as the diphenylamine derivative.

(Reference Example 4)
An organic EL device was produced after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (D) was used as the diphenylamine derivative.
(Reference Example 5)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (E) was used as the diphenylamine derivative.
(Reference Example 6)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (F) was used as the diphenylamine derivative.

(Comparative Example 1)
[Preparation of hole transport material]
Compound (H) 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 compound (I) in water to obtain a hole transport material.
As the compound (I), 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]
The hole transport material was prepared by mixing the compound (A) and the polycarbonate resin (manufactured by Teijin Chemicals Ltd., “Panlite L-1250”) at a weight ratio of 3: 7 to dichloroethane.
[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 4)
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 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 (G) was used as the diphenylamine derivative.

(Comparative Example 6)
An organic EL device was manufactured after preparing a hole transporting material in the same manner as in Example 2 except that the compound (G) was used as the diphenylamine derivative.
(Comparative Example 7)
An organic EL device was manufactured after preparing a hole transport material in the same manner as in Reference Example 1 except that the compound (G) was used as the diphenylamine derivative.

3. Evaluation For each of the organic EL elements of each example, each reference example and each comparative example, the light emission luminance (cd / m ² ) and the maximum light emission efficiency (lm / W) were measured, and the light emission luminance was reduced to half of the initial value. The time (half-life) was measured.
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.
And each measured value (luminescence brightness, maximum luminous efficiency, half-life) measured in Comparative Example 1 as a reference value, each measured value measured in each Example, each Reference Example and each Comparative Example, Evaluation was performed according to the following four-stage 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 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.

Moreover, as for the organic EL element of each Example, all showed the tendency for the maximum luminous efficiency to be improved compared with the organic EL element of each reference example. This was a result suggesting that the separation distance of the main skeleton was maintained at a more appropriate distance by adding the urethane (meth) acrylate-based crosslinking agent.
In addition, it showed the tendency for the improvement of maximum luminous efficiency to be recognized notably, so that the length of a urethane (meth) acrylate type crosslinking agent was more suitable.

Further, Examples 2, 7, 10, 13, 16 in which the mixing ratio of the compound represented by the general formula (1) and the urethane (meth) acrylate-based crosslinking agent was formed by a particularly appropriate hole transport material. The organic EL devices of No. 19 and No. 19 exhibited a tendency to exhibit particularly excellent emission luminance improvement, maximum emission efficiency improvement, and half-life extension.
Further, by appropriately selecting the substituent X, in each example, the longer the main skeleton separation distance is maintained, the better the emission luminance, the maximum emission efficiency, and the half-life. A result indicating an extension of was obtained.

  Moreover, the said Example except having used the compound which has a methacryloyl group as a functional group of the substituent X as a compound represented by the said General formula (1), and using the urethane methacrylate compound as a urethane (meth) acrylate type crosslinking agent. A hole transport material was prepared in the same manner as in 1 to 20 to produce an organic EL device. These organic EL elements were evaluated in the same manner as in the above evaluation method, but the same results as described above were 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 ... Input / output terminal for data communication 1430 ... Television monitor 1440 ... Personal computer

Claims (23)

The composition for electroconductive materials characterized by containing the compound represented by following General formula (1), and a urethane (meth) acrylate type crosslinking agent.

[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. ]

[Wherein, n represents an integer of 2 to 8, and Z represents a hydrogen atom or a methyl group. ]   The urethane (meth) acrylate crosslinking agent is at least one of an aromatic urethane (meth) acrylate crosslinking agent, an alicyclic urethane (meth) acrylate crosslinking agent, and an aliphatic urethane (meth) acrylate crosslinking agent. The composition for conductive materials according to claim 1, comprising:   The composition for conductive materials according to claim 1, wherein the urethane (meth) acrylate-based crosslinking agent has at least two (meth) acryloyl groups. The composition for conductive materials according to claim 3, wherein the urethane (meth) acrylate-based crosslinking agent contains a compound represented by the following general formula (3) as a main component.

[Wherein, n represents an integer of 1 to 100, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different, and may represent two A ^2. Each independently represents a group obtained by removing two isocyanate groups from a diisocyanate compound and may be the same or different. ] The composition for conductive materials according to claim 4, wherein the urethane (meth) acrylate-based cross-linking agent contains a compound represented by the following general formula (4) as a main component.

[Wherein, n represents an integer of 1 to 90, and two A ^{1 s} each independently represent a hydrogen atom or a methyl group, and may be the same or different. ] Wherein the substituent X ¹ and the substituent X ^3, claim 1 to a conductive material composition according to any one of the 5 identical. The composition for a conductive material according to claim 1, wherein the substituent X ² and the substituent X ⁴ are the same. The composition for a conductive material 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 claim 1.   The composition for a conductive material according to claim 1, wherein the group Y is composed of a carbon atom and a hydrogen atom.   The composition for a conductive material according to claim 1, wherein the total number of carbon atoms of the group Y is 6 to 30.   The composition for conductive materials according to any one of claims 1 to 11, wherein in the group Y, the number of the aromatic hydrocarbon rings is 1 to 5.   The composition for a conductive material according to any one of claims 1 to 12, wherein the group Y is a biphenylene group or a derivative thereof. Any ^{one of} the substituent X ¹ , the substituent X ² , the substituent X ³ and the substituent X ⁴ between the compounds represented by the following general formula (1) is directly or via a urethane (meth) acrylate-based crosslinking agent. A conductive material obtained by polymerization reaction.

[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. ]

[Wherein, n represents an integer of 2 to 8, and Z represents a hydrogen atom or a methyl group. ]   The conductive material according to claim 14, wherein the compound and the urethane (meth) acrylate-based crosslinking agent undergo 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 14 or 15 as a main material.   The conductive layer according to claim 16 or 17, wherein the conductive layer is a hole transport layer.   The conductive layer according to claim 18, 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 16.   The electronic device according to claim 20, wherein the electronic device is a light emitting element or a photoelectric conversion element.   The electronic device according to claim 21, wherein the light emitting element is an organic electroluminescence element. An electronic apparatus comprising the electronic device according to any one of claims 20 to 22.

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