KR20150016507A - Method for producing conductive thin film laminate - Google Patents

Abstract

The present invention relates to a method of producing a conductive thin film laminate comprising a substrate and a conductive thin film formed on the substrate, wherein the conductive thin film is formed by coating the conductive thin film precursor on a substrate or on a conductive thin film formed on the substrate, . The substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm and a product of a wavelength in a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 탆 ² or more and 16 탆 ² or less.

Description

METHOD FOR PRODUCING CONDUCTIVE THIN FILM LAMINATE [0002]

The present invention relates to a method for producing a conductive thin film laminate, a conductive thin film laminate obtained by the method, and an organic electroluminescence device, an organic electroluminescence (EL) display, and an organic EL light.

BACKGROUND ART [0002] Recent developments regarding the conductive thin film laminate are under development in the field of TFT, solar cell, organic EL display, and organic EL illumination. Particularly, the wet film forming method is advantageous from the viewpoint of utilization efficiency of material, manufacturing cost, and large area compared to vacuum vapor deposition. Further, by forming a composition by mixing various kinds of materials, there is an advantage that flexibility can be imparted to the design of the material. In the wet film formation method, it is necessary to dissolve or disperse various materials in the solvent, and it is necessary to remove the solvent at the time of forming the thin film. Therefore, several methods for removing the solvent have been proposed.

In Patent Documents 1 to 4, it is described that heating using electromagnetic waves, particularly infrared rays, is effective. It is also believed that by heating, the denseness of the thin film is imparted to improve the strength and conductivity of the thin film. In addition, when the conductive thin film has a crosslinkable group, it is crosslinked by heating and becomes insoluble in a solvent, so that the functional layer can be laminated by further application.

Japanese Patent Application Laid-Open No. 2008-091316 Japanese Patent Application Laid-Open No. 2008-226642 International Publication No. 2006/070713 Japanese Patent Application Laid-Open No. 2004-127897

However, in a conductive thin film having a film thickness of less than 1 占 퐉, simple electromagnetic wave heating severely damaged the conductive thin film, failing to achieve expected performance. Further, when the conductive thin film has a crosslinkable group, it takes a long time to crosslink the crosslinkable group, and the required amount of energy is large, so that it has been desired to suppress the production cost.

It is an object of the present invention to provide a method of manufacturing a conductive thin film laminate which solves the above problems. And an object of the present invention is to provide an organic electroluminescent device having a low driving voltage, a high luminous efficiency and a long driving life, and an organic EL display and an organic EL lighting device having the same.

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems and found that the present invention solves the problem by heating the conductive thin film using infrared rays as a heating means in particular, thereby completing the present invention.

That is, the present invention is based on the following points [1] to [36].

[1] A method for producing a conductive thin film laminate comprising a substrate and a conductive thin film formed on the substrate,

The conductive thin film is formed by applying a conductive thin film precursor containing a polymer compound having a repeating unit represented by the following formula (1) and having a crosslinking group on a substrate or on a conductive thin film formed on the substrate, Wherein the conductive thin film laminate is formed by crosslinking.

[Chemical Formula 1]

(In the formula (1), Ar ^a or Ar ^b each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group having 4 to 60 carbon atoms which may have a substituent.)

[2] The process for producing a conductive thin film laminate according to [1], wherein the crosslinking group is a crosslinking group selected from the following <crosslinkable group T>.

&Lt; Crosslinkable group T &

(2)

(Wherein R ²¹ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group which may have an Ar ⁴¹ substituent, or an aromatic heterocyclic group which may have a substituent. The ring may have a substituent.)

[3] The method for producing a conductive thin film laminate according to [2], wherein the crosslinkable group is a benzocyclobutene ring represented by the following formula (3).

(3)

[4] The method for producing a conductive thin film laminate according to any one of [1] to [3], wherein the conductive thin film precursor contains a polymer compound containing a repeating unit represented by the following formula (2).

[Chemical Formula 4]

Ar ²¹ and Ar ²² each independently represent an aromatic hydrocarbon group which may have a direct bond or a substituent or an aromatic heterocyclic group which may have a substituent and Ar ²³ to Ar ²³ each independently represent an aromatic heterocyclic group which may have a substituent, Ar ²⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent and T ² represents a crosslinkable group.

[5] The method for producing a conductive thin film laminate according to any one of [1] to [4], wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (4).

[Chemical Formula 5]

(In the formula (4), Ar ₆ and Ar ₇ each independently represent a bivalent aromatic ring group which may have a substituent, Ar ₈ represents a aromatic ring group which may have a substituent, and R ₈ and R ₉ each independently A hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent group, R ₈ and R ₉ are bonded to each other to form a ring P represents an integer of 1 to 5).

[6] The method for producing a conductive thin film laminate according to any one of [1] to [5], wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (6).

[Chemical Formula 6]

(Formula (6) ^{of, Ar 31, Ar 33, Ar} 34 and Ar ³⁵ each independently represents a divalent aromatic heterocyclic ring which may contain a divalent aromatic hydrocarbon ring group or a substituent which may have a substituent, Ar ³² is An aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic ring which may have a substituent.

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent and R ¹² to R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms An alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

R ¹² and R ¹³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ may combine with each other to form a ring. R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring.

l, m and n each independently represents an integer of 0 to 2.)

[7] The substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm,

The production of the conductive thin-film laminate according to any one of the above [1] to [6], wherein a product (a) of a wavelength in a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is not less than 2 탆 ^{2 and not} more than 16 탆 ² Way.

[8] The method for producing a conductive thin film laminate according to any one of [1] to [7], wherein a minimum value of an infrared ray transmittance of the substrate is 95% or less.

[9] The method for producing a conductive thin film laminate according to any one of [1] to [8], wherein a peak wavelength of infrared rays is 0.8 탆 or more and 25 탆 or less.

The conductive thin film precursor as described in [1] above, wherein the substrate is heated at a temperature of 150 ° C. or more and 300 ° C. or less in infrared irradiation, and a holding time in the temperature range is 5 seconds or more and 30 minutes or less, To (9) above.

Wherein the conductive thin film precursor is heated at a temperature of 150 ° C. or more and 300 ° C. or less in the infrared irradiation of the substrate and the time for which the substrate is maintained at a constant temperature in the temperature range is 20 seconds or more and 15 minutes or less, The method for producing a conductive thin film laminate according to any one of [1] to [10].

[12] The method for producing a conductive thin film laminate according to any one of [1] to [11], wherein the substrate is heated by infrared rays at a heating rate of not less than 10 ° C./min and not more than 250 ° C./min.

(13) When the product of the wavelength at the minimum value of the infrared ray transmittance of the substrate and the peak wavelength of the infrared ray and the holding time t (seconds) at the substrate temperature of 150 ° C or higher satisfy the following formula The conductive thin film laminate according to any one of the above [1] to [12]

0.002?? / T (? ² / s)? 0.2 (7)

[14] A method for producing a conductive thin film laminate, wherein the conductive thin film formed on the substrate and the substrate has a thickness of 50 nm or more and 1 μm or less,

The conductive thin film is formed by applying a conductive thin film precursor containing a polymer compound having a repeating unit represented by the following formula (1) and having a crosslinking group on a substrate or on a conductive thin film formed on the substrate, Wherein the conductive thin film laminate is formed by crosslinking.

(7)

(In the formula (1), Ar ^a or Ar ^b each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group having 4 to 60 carbon atoms which may have a substituent.)

[15] The method for producing a conductive thin film laminate according to [14], wherein the crosslinking group is a crosslinking group selected from the following <crosslinkable group T>.

&Lt; Crosslinkable group T &

[Chemical Formula 8]

(Wherein R ²¹ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar ⁴¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. The butene ring may have a substituent.)

[16] The method for producing a conductive thin film laminate according to [15], wherein the crosslinkable group is a benzocyclobutene ring represented by the following formula (3).

[Chemical Formula 9]

[17] The method for producing a conductive thin film laminate according to any one of [14] to [16], wherein the conductive thin film precursor contains a polymer compound containing a repeating unit represented by the following formula (2).

[Chemical formula 10]

Ar ²¹ and Ar ²² each independently represent an aromatic hydrocarbon group which may have a direct bond or a substituent or an aromatic heterocyclic group which may have a substituent and Ar ²³ to Ar ²³ each independently represent an aromatic heterocyclic group which may have a substituent, Ar ²⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent and T ² represents a crosslinkable group.

[18] The method for producing a conductive thin film laminate according to any one of [14] to [17], wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (4).

(11)

(In the formula (4), Ar ₆ and Ar ₇ each independently represent a divalent aromatic ring group which may have a substituent, Ar ₈ represents a aromatic ring group which may have a substituent, and R ₈ and R ₉ each independently A hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent group, R ₈ and R ₉ are bonded to each other to form a ring P represents an integer of 1 to 5).

[19] The method for producing a conductive thin film laminate according to any one of [14] to [18], wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (6).

[Chemical Formula 12]

(Formula (6) ^{of, Ar 31, Ar 33, Ar} 34 and Ar ³⁵ each independently represents a divalent aromatic heterocyclic ring which may contain a divalent aromatic hydrocarbon ring group or a substituent which may have a substituent, Ar ³² is An aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic ring which may have a substituent.

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent and R ¹² to R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms An alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

R ¹² and R ¹³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ may combine with each other to form a ring. R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring.

l, m and n each independently represents an integer of 0 to 2.)

[20] The substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm,

The production of a conductive thin film laminate according to any one of the above [14] to [19], wherein a product (a) of a wavelength at a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 탆 ² or more and 16 탆 ² or less Way.

[21] The production method of a conductive thin film laminate according to any one of [14] to [20], wherein a minimum value of the infrared ray transmittance of the substrate is 95% or less.

[22] The production method of a conductive thin film laminate according to any one of [14] to [21], wherein a peak wavelength of infrared rays is 0.8 탆 or more and 25 탆 or less.

Wherein the conductive thin film precursor is heated at a temperature of not less than 70 ° C. and not more than 300 ° C. at the time of irradiating the substrate with infrared light and the time for which the substrate is held in the temperature range is not less than 5 seconds and not more than 30 minutes, (14) to (22).

When the conductive thin film precursor is heated at a temperature of 70 ° C. or more and 300 ° C. or less in the infrared irradiation of the substrate, the time for which the substrate is maintained at a constant temperature in the temperature range is 20 seconds or more and 15 minutes or less A method for producing a conductive thin film laminate according to any one of [14] to [23] above.

[25] The method for producing a conductive thin film laminate according to any one of [14] to [24], wherein the substrate is heated by infrared rays at a heating rate of 10 ° C./min or more and 250 ° C./min or less.

When the product of the wavelength at the minimum value of the infrared ray transmittance of the substrate and the peak wavelength of the infrared ray and the time at which the infrared ray is irradiated (t: second) satisfy the relation of the following formula (7) A method for producing a conductive thin film laminate according to any one of [14] to [25] above.

0.002?? / T (? ² / s)? 0.2 (7)

[27] A method for producing a conductive thin film laminate, comprising a substrate and a conductive thin film formed on the substrate,

The conductive thin film precursor contains a light emitting material,

Applying an ink containing the light emitting material and a solvent on a substrate or on a conductive thin film formed on the substrate and then heating the substrate at a temperature of 150 DEG C or less by infrared rays,

Wherein the temperature of the substrate is maintained at not less than 70 DEG C and not more than 150 DEG C for not less than 5 seconds and not more than 20 minutes at the time of infrared irradiation.

Wherein the conductive thin film precursor is heated at a temperature of not less than 70 ° C. and not more than 150 ° C. at the time of irradiating the substrate with infrared rays and the time for which the substrate is maintained at a constant temperature in the temperature range is not less than 20 seconds and not more than 10 minutes, The method for producing a conductive thin film laminate according to [27].

[29] The method for producing a conductive thin film laminate according to the above [27] or [28], wherein the substrate is heated by infrared rays at a heating rate of 10 ° C / min or more and 250 ° C / min or less.

[30] The ink according to any one of [27] to [29], wherein the difference (t = t1 - t2) between the boiling point t1 of the solvent contained in the ink and the maximum temperature t2 of the substrate temperature is 5 [ A method for producing a thin film laminate.

[31] The method for producing a conductive thin film laminate according to any one of [27] to [30], wherein the solvent contained in the ink has a boiling point of 75 ° C or more and 350 ° C or less.

When the product of the wavelength at the minimum value of the infrared ray transmittance of the substrate and the peak wavelength of the infrared ray and the holding time t (seconds) at the substrate temperature of 70 ° C. or higher satisfy the following formula The conductive thin film laminate according to any one of the above [27] to [31], wherein the conductive thin film laminate satisfies the following relationship:

0.003?? / T (? ² / s)? 0.5 (8)

[33] A conductive thin film laminate obtained by the method according to any one of [1] to [32] above.

[34] An organic electroluminescent device comprising the conductive thin film laminate according to [33].

[35] An organic EL display comprising the organic electroluminescent device according to [34].

[36] An organic EL light including the organic electroluminescent device according to [34].

According to the present invention, the conductive thin film laminate can be obtained by heating for a short time without damaging the conductive thin film. The resultant conductive thin film laminate has high conductivity, and in particular, the organic electroluminescent device is not only an element having a high luminous efficiency and a low driving voltage, but also exhibits a reduction in light emission luminance, a rise in voltage, and a non-light emitting portion (dark spot) Short-circuit defects, and the like are suppressed.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing a structural example of an organic electroluminescent device. Fig.
Fig. 2 is a graph showing the relationship between the initial film thickness and the residual film ratio of the composition for forming a hole injection layer obtained in Example 8 and Comparative Example 6. Fig.
Fig. 3 is a graph showing the relationship between the heating time and the residual film ratio of the composition for forming a hole injection layer obtained in Example 9. Fig.
4 is a graph showing the relationship between the initial film thickness and the residual film ratio of the composition for forming a hole injection layer obtained in Example 10 and Comparative Example 7. Fig.

Hereinafter, embodiments of the present invention will be described in detail. The description of constituent requirements described below is an example of the embodiment of the present invention, and is not limited to these contents unless the object of the present invention is overcome.

The present invention provides a method for producing a conductive thin film laminate comprising a substrate and a conductive thin film formed on the substrate, wherein the conductive thin film is formed by applying the conductive thin film precursor on a substrate or on a conductive thin film formed on the substrate, And is formed by heating.

Wherein the substrate has a minimum value of infrared transmittance in a wavelength range of 2000 to 3300 nm and a product of a wavelength in a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 탆 ² or more and 16 탆 ² or less.

1. Substrate

In the present invention, inorganic glass or various resins can be used for the substrate used in the conductive thin film laminate. For example, inorganic glass such as alkali-free glass, glass plate glass, quartz glass, and borosilicate glass, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), cellulose acetate propionate, polyether sulfone, polycarbonate, , Polyamide, and the like. Further, a metal plate, a metal foil and the like can also be used. It is preferably an inorganic glass.

The thickness of the substrate is usually 0.01 mm or more, preferably 0.1 mm or more, and more preferably 0.2 mm or more. It is usually 10 mm or less, preferably 5 mm or less, and more preferably 1 mm or less.

If the thickness of the substrate is within the above range, the substrate can be removed from the heat of the conductive thin film that has been excessively heated by infrared rays, so that breakage of the conductive thin film can be suppressed. Further, the substrate is appropriately heated, and the conductive thin film is heated by the heat. That is, the conductive thin film can be appropriately heated with the thickness of the substrate, and the performance of the conductive thin film can be enhanced.

2. Conductive thin film (precursor)

In the present invention, the conductive thin film is disposed and laminated on the substrate. A plurality of conductive thin films may be stacked. The conductive thin film may be any film having conductivity, but is usually 10 M? /? Or less, preferably 1 M? /? Or less, more preferably 1000? / ?, particularly preferably 500? Or less. The thickness of the conductive thin film is usually 3 nm or more, preferably 5 nm or more, more preferably 8 nm or more, and usually 1 占 퐉 or less, preferably 800 nm or less, more preferably 500 nm or less, And preferably 400 nm or less.

The conductive thin film precursor refers to a composition prepared at the time of forming the conductive thin film. The composition is a composition containing a conductive material, and the details will be described later.

3. Conductive thin film laminate

In the present invention, the conductive thin film laminate has a structure in which a conductive thin film is disposed and laminated on a substrate. A method of arranging and laminating a conductive thin film on a substrate can be achieved by applying a composition containing a conductive thin film precursor, for example, a conductive material, onto the substrate, and heating the applied thin film precursor by infrared rays after application. In the case of laminating the conductive thin film, the conductive thin film precursor is applied on the conductive thin film formed on the substrate in advance, and then heated by infrared rays after application. In the present invention, by using infrared rays, it is possible to manufacture a conductive thin film laminate having the above effect in a short time. In addition, compared with the use of a hot air furnace or a hot plate, firing in a short time is possible, and the effect of gas (oxygen and moisture) and dust can be minimized.

4. Infrared heating

For infrared heating, a halogen heater or a ceramic-coated halogen heater, a ceramic heater, or the like can be used. Examples of the halogen heater include a halogen heater manufactured by Ushio Corporation (UH-USC, UH-USD, UH-MA1, UH-USF, UH- USP, UH- USPN, and a ceramic coat (black coat) , Manufactured by Heraeus Co., Ltd., and the like. The far infrared ray heater is, for example, a far-infrared panel type clean heater manufactured by AMK.

As a heating method, for example, a method in which the infrared heater is provided on the top of the substrate and infrared heating is performed can be exemplified.

During infrared heating, it is preferable that the infrared transmission of the substrate has a minimum value in the wavelength range of 2000 nm to 3300 nm. The upper limit of the infrared transmittance is usually 95% or less, preferably 90% or less, more preferably 85% or less, further preferably 80% or less, particularly preferably 75% or less. The lower limit value is usually 5% or more, preferably 10% or more, more preferably 20% or more, further preferably 25% or more.

In the above range, the substrate is suitably heated and the conductive thin film precursor is heated by the heat conduction. That is, the conductive thin film precursor can be appropriately heated with the thickness of the substrate, and the performance of the conductive thin film can be enhanced. In addition, even when the conductive thin film precursor is heated excessively, it may become a desire to lose heat moderately.

The lower limit value of the peak wavelength of the infrared heater is usually 0.8 占 퐉 or more, preferably 0.9 占 퐉 or more, more preferably 1 占 퐉 or more, particularly preferably 1.1 占 퐉 or more. The upper limit value thereof is 25 占 퐉 or less, preferably 10 占 퐉 or less, more preferably 5 占 퐉 or less, particularly preferably 3 占 퐉 or less.

Within this range, the conductive thin film precursor can be heated by absorbing infrared rays. Further, the substrate is suitably heated by the peak wavelength of the infrared heater in this range, and the conductive thin film precursor can be heated with the heat. When an organic material is used for the conductive thin film precursor, the organic material absorbs the infrared rays of the infrared ray heater and can heat the conductive thin film precursor by infrared ray induction heating.

In the combination of the substrate and the infrared ray, as described above, the infrared ray transmittance of the substrate has a minimum value of the transmittance in the wavelength range of 2000 to 3300 nm, and the product of the wavelength in the minimum value and the peak wavelength of the infrared heater (?) has a lower limit value of usually 2 占 퐉 ² or more, preferably 2.5 占 퐉 ² or more, more preferably 3 占 퐉 ² or more. The upper limit value is usually not more than 16 탆 ² , preferably not more than 15.5 탆 ² , more preferably not more than 15 탆 ² .

When the product of the wavelength at the minimum value of the infrared ray transmittance of the substrate and the peak wavelength of the infrared heater is within this range, the conductive thin film precursor can be suitably heated and the performance of the conductive thin film can be enhanced.

Hereinafter, the reason why the product (?) Of the wavelength at the minimum value of the infrared ray transmittance of the substrate and the peak wavelength of the infrared heater is used as a parameter for specifying the invention will be described below.

The wavelength of the minimum value in the range of 2000 to 3300 nm in the infrared absorption of the substrate can be appropriately heated without excessively heating the substrate. An infrared heater for heating the substrate is a typical value indicating the characteristic, and may be the peak wavelength of the infrared heater. The relationship between the wavelength and the energy is in inverse proportion, and therefore, the smaller the value of this parameter (?), The larger the energy that can be obtained from the substrate. In addition, the larger the value of the parameter?, The lower the energy obtained by the substrate. In the present invention, since it is necessary to appropriately heat the conductive thin film precursor, if the substrate is properly heated and the conductive thin film is excessively heated, it becomes a hot bath, and when it is not heated well, it is necessary to apply heat from the substrate to the conductive thin film It becomes. This parameter is the index in the present invention.

5. Polymer compound

Hereinafter, the polymer compound as a preferable compound included in the conductive thin film will be described.

The polymer compound of the present invention includes a repeating unit represented by the following formula (1).

[Chemical Formula 13]

(In the formula (1), Ar ^a and Ar ^b each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group having 4 to 60 carbon atoms which may have a substituent.)

As the aromatic hydrocarbon ring group, for example, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a triphenylene ring, a chrysene ring, a naphthacene ring, a perylene ring, Monocyclic or two to five condensed rings of 5 or 6-membered rings such as a furan ring, a coronene ring, an acenaphthene ring, a fluoranthene ring and a fluorene ring, and rings in which a plurality of these rings are directly bonded. Herein, in the present invention, the term "free valency" refers to a compound capable of forming a bond with another free valence as described in the Organic Chemistry / Biochemistry Nomenclature (Phase) (Second Edition, Nankodo, published in 1992). That is, for example, "a benzene ring having one free valence" refers to a phenyl group, and a "benzene ring having two free valences" refers to a phenylene group.

Examples of the aromatic heterocyclic group include groups having one or two free valences such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole And examples thereof include a ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthrene ring, a benzoimidazole ring, Monocyclic or two to four condensed rings of 5 or 6-membered heterocyclic rings such as a pyran ring, a pyran ring, a pyran ring, a pyrimidine ring, a quinazoline ring, a quinazolinone ring, an azulene ring and the like, There may be mentioned a ring, and the like.

Here, when the aromatic hydrocarbon ring group or aromatic heterocyclic ring group is a condensed ring having one or two free valences, the number of the condensed rings is preferably small in view of the high stability of the ring, and preferably not more than eight , And it is more preferable that the number is 5 or less. On the other hand, the lower limit is two. Specific examples of the aromatic hydrocarbon ring group or aromatic heterocyclic ring group include naphthalene rings, anthracene rings, and naphthalene rings each having one or two free valences in terms of solubility and heat resistance, such as benzene ring, thiophene ring and pyridine ring, A condensed ring such as a phenanthrene ring, a triphenylene ring and a pyrene ring, and an aromatic hydrocarbon ring in which 2 to 8 aromatic rings such as a fluorene ring, biphenyl, terphenyl and the like are connected are preferable. Of these, benzene rings, fluorene rings, biphenyl, and terphenyl, each having one or two free valences, are more preferred because of their high solubility and high stability.

Examples of the substituent that the aromatic hydrocarbon ring group or aromatic heterocyclic group may have include a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon ring group having 6 to 25 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, (Hetero) aryloxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, (hetero) arylthio groups having 3 to 20 carbon atoms, cyano groups, and the like, . Among them, a saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon ring group having 6 to 25 carbon atoms are preferable in view of solubility and heat resistance.

Specific examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Hexyl group, decyl group and octadecyl group. Among these, methyl group, ethyl group and isopropyl group are preferable, and methyl group and ethyl group are more preferable in view of easiness of obtaining raw material and low cost.

Examples of the monovalent aromatic hydrocarbon ring group having 6 to 25 carbon atoms include a naphthyl group such as phenyl group, 1-naphthyl group and 2-naphthyl group, a phenanthyl group such as 9-phenanthyl group and 3-phenanthyl group, Anthryl groups such as anthryl groups and 9-anthryl groups, naphthacenyl groups such as 1-naphthacenyl group and 2-naphthacenyl group, 1-chrysenyl group, 2- , A 4-chrysenyl group, a 5-chrysenyl group and a 6-clicenyl group, a pyrenyl group such as a 1-pyrenyl group, a triphenylrenyl group such as a 1-triphenylrenyl group, A biphenyl group such as a 4-biphenyl group and a 3-biphenyl group, a group having a fluoranthene ring, a group having a fluorene ring, a group having an acenaphthene ring, a substituent having a benzpyrene ring, etc. . Among them, phenyl group, 2-naphthyl group and 3-biphenyl group are preferable from the viewpoint of stability of the compound, and phenyl group is particularly preferable from the easiness of purification.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include a thienyl group such as 2-thienyl group, a furyl group such as 2-furyl group, an imidazolyl group such as 2-imidazolyl group, A pyridyl group such as a 2-pyridyl group, and a triazinyl group such as a 1,3,5-triazin-2-yl group. Among them, a carbazolyl group, particularly a 9-carbazolyl group, is preferable from the standpoint of stability.

Examples of the diarylamino group having 12 to 60 carbon atoms include a diphenylamino group, an N-1-naphthyl-N-phenylamino group, an N-2-naphthyl-N-phenylamino group, , An N- (biphenyl-4-yl) -N-phenylamino group, and a bis (biphenyl-4-yl) amino group. Among them, a diphenylamino group, an N-1-naphthyl-N-phenylamino group and an N-2-naphthyl-N-phenylamino group are preferable, and a diphenylamino group is particularly preferable in view of stability.

Examples of the alkyloxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group, and an octadecyloxy group.

Examples of the (hetero) aryloxy group having 3 to 20 carbon atoms include substituents having a heteroaryloxy group such as an aryloxy group such as a phenoxy group, a 1-naphthyloxy group, a 9-anthraniloxy group and a 2-thienyloxy group, have.

Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an isopropylthio group and a cyclohexylthio group.

Examples of the (hetero) arylthio group having 3 to 20 carbon atoms include arylthio groups such as phenylthio group, 1-naphthylthio group and 9-anthranthylthio group, and heteroarylthio groups such as 2-thienylthio group and the like .

When the polymer compound in the present invention has an arylamino group in which the aromatic hydrocarbon ring group or the aromatic heterocyclic group is bonded to a group other than the aromatic heterocyclic group, the group other than the aromatic hydrocarbon ring group or aromatic heterocyclic group is preferably an alkylene group having 1 to 70 carbon atoms Aliphatic hydrocarbon groups are preferred. The aliphatic hydrocarbon group may be in a chain form, in a ring form, in a saturated form or in an unsaturated form.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, an octyl group, a cyclohexyl group, , Octadecyl group, and the like. Of these, the number of carbon atoms such as methyl, 1,2-ethyl, 1,3-propyl, 1,4-butyl, 1,5-pentyl and 1,8- Preferably a group of 1 to 10 carbon atoms, more preferably a group of 1 to 8 carbon atoms. In addition, a group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and an isopropyl group is particularly preferable, and a group having 1 to 2 carbon atoms such as a methyl group and an ethyl group is most preferable. The aliphatic hydrocarbon group is preferably a saturated hydrocarbon group in terms of oxidation-reduction durability.

The aliphatic unsaturated hydrocarbon group is preferably an alkenylene group, and specific examples thereof include a 1,2-vinylene group, a 1,3-propenylene group, a 1,2-propenylene group and a 1,4-butenylene group, . Among them, the vinylene group is particularly preferable because the plane of the molecule is improved in planarity to diffuse the conjugate plane, and the charge becomes non-stationary and the stability of the compound tends to be enhanced. The number of carbon atoms of the unsaturated aliphatic hydrocarbon group is preferably 2 or more from the viewpoints of planarity and charge diffusion, more preferably 10 or less, and further preferably 6 or less.

The number of carbon atoms contained in the aliphatic hydrocarbon group is preferably large in terms of increasing the solubility, while it is preferable in view of the stability of the compound and the film density. Specifically, the number of carbon atoms is typically at least 1, preferably at least 4, more preferably at least 6, and usually at most 70, preferably at most 60, more preferably at most 36.

As the polymer compound in the present invention, a structure such as a polymer having a repeating unit represented by the following formulas (11), (12), (13) and (14) is more preferable.

A polymer having a repeating unit represented by the following formula (11) is synthesized by a reaction that forms an N-Ar bond such as a Buchwald-Hartwig reaction or an Ulmann reaction.

[Chemical Formula 14]

In formula (11), Ar ¹ to Ar ³ each independently represent the same aromatic hydrocarbon ring group or aromatic heterocyclic group as described above, and Z represents a divalent group, preferably -CR ¹ R ² -, -CO-, Represents a group connecting 1 to 24 groups selected from the group consisting of -O-, -S-, -SO ₂ -, and -SiR ³ R ⁴ -. R ¹ to R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group or an aromatic heterocyclic group as defined above, R ¹ and R ² , R ³ and R ⁴ represent They may be combined with each other to form a ring. a represents an integer of 0 to 8; When a is an integer of 2 to 8, Ar ³ and Z may be different from each other. n represents the number of repeating units.

Formula (M1-1) ~ formula (M1-3) ^{of, Ar 1 ~ Ar 3, Z} , a is the same meaning as defined in the formula (11). b represents an integer of 0 to 8; X ¹ represents a sulfonate ester group such as a halogen atom or a trifluoromethanesulfonyloxy group (CF ₃ SO ₂ O-).

The monomers represented by the formulas (M1-1) to (M1-3) may be used singly or two or more of them may be used independently, and ten or less monomers are preferred.

When two or more of Ar ¹ to Ar ³ , Z, a and X ¹ are present in the formulas (11) and (M1-1) to (M1-3), they may be different from each other.

The polymer having a repeating unit represented by the following formula (12) is synthesized by a reaction that forms an Ar-Ar bond such as a Yamamoto reaction, a Negishi reaction, a Migita-Kosugi-Stile reaction, or a Suzuki-Miyaura reaction.

[Chemical Formula 15]

Ar ¹ to Ar ³ , Z, a, b, X ¹ and n in the formulas (12), (M2-1) and (M2-2) (M1-3).

Formula (M2-2) of the, G is, if the Negishi reaction, if the zinc atom, Migita-Kosugi-Stile reaction having a substituent such as BrZn-, (CH _{3) 3} the tin atoms, Suzuki- having a substituent such as Sn- In the case of the Miyaura reaction, a boron atom having a substituent such as (RO) ₂ B- (R represents a hydrogen atom or an alkyl group which may be bonded to each other to form a ring).

When two or more of Ar ¹ to Ar ³ , Z, a, b and X ¹ are present in the formulas (12), (M2-1) and (M2-2), they may be different from each other.

A polymer having a repeating unit represented by the following formula (13) is synthesized by a reaction that forms an O-Ar bond or an S-Ar bond.

[Chemical Formula 16]

Ar ¹ to Ar ³ , Z, a, b, X ¹ and n in formulas (13), (M3-1) and (M3-2) (M1-3).

In the formulas (13) and (M3-2), Q ¹ represents an oxygen atom or a sulfur atom.

When two or more of Ar ¹ to Ar ³ , Z, a, b, Q ¹ and X ¹ are present in the formulas (13), (M3-1) and (M3-2) do.

A polymer having a repeating unit represented by the following formula (14) is synthesized by a reaction for forming an ester bond or an amide bond.

[Chemical Formula 17]

Ar ¹ to Ar ³ and Z, a, b and n in the formula (14), the formula (M4-1) and the formula (M4-2) satisfy the formula (11) 3). &Lt; / RTI &gt;

Q ² represents a carbonyl group or a sulfonyl group; Q ³ represents an oxygen atom, a sulfur atom, or an -NR ⁵ - group (R ⁵ represents a hydrogen atom, an alkyl group, A hydrogen atom, an alkyl group which may have a substituent, the same aromatic hydrocarbon ring group or an aromatic heterocyclic group as described above), and X ² represents a halogen atom.

When two or more of Ar ¹ to Ar ³ , Z, a, b, Q ² and Q ³ are present in the formulas (14), (M4-1) and (M4-2) do.

Among them, polymers having repeating units represented by formulas (11) and (12) are preferable as the polymer compound in the present invention, and polymers having repeating units represented by formula (11) . In the formulas (11) to (14), a is preferably 0 in terms of excellent hole injection transportability. Further, a is preferably 1 or 2, and more preferably 1, in view of a wide band gap and an excellent hole transporting property. And -CR ¹ R ² - is preferable because Z is excellent in durability.

In the case of a compound having no crosslinkable group as the polymer compound in the present invention, for example, PEDOT / PSS (Adv. Mater., 2000, vol. 12, p. 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, vol. 94, page 7716).

<Insolence>

The polymer compound according to the present invention preferably has an insolubilizing group. The insolubilizer is preferably a crosslinkable group or a dissociation group. It is preferable that the insolubilizing group is a crosslinking group because it chemically bonds three-dimensionally.

&Lt; Cross-linking agent &

The polymer compound according to the present invention preferably has a crosslinkable group.

Here, the crosslinkable group refers to a group which reacts with the same or different groups of other molecules located near by irradiation of heat and / or active energy rays to generate a new chemical bond.

Since the polymer compound has a crosslinkable group, after the application, these crosslinkable groups can be used for crosslinking to insolubilize the conductive thin film. Thus, the functional thin film can be further laminated on the conductive thin film layer by application.

The crosslinkable group is selected from the following <crosslinkable group T> for ease of bonding.

&Lt; Crosslinkable group T &

[Chemical Formula 18]

In the formula, R ²¹ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Ar ⁴¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

The benzocyclobutene ring may have a substituent.

As the crosslinkable group, a cationic polymerizable group such as a cyclic ether group such as an epoxy group or an oxetane group, or a vinyl ether group is preferable because of high reactivity and easy crosslinking to an organic solvent. Of these, an oxetane group is particularly preferable in view of easy control of the rate of cationic polymerization, and a vinyl ether group is preferable in that a hydroxyl group which may cause deterioration of the device during cationic polymerization is not generated well.

The crosslinkable group is preferably a group such as an aryl vinyl carbonyl group such as a cinnamoyl group, a group which reacts with a cyclization group such as a benzocyclobutene ring, from the viewpoint of further improving the electrochemical stability, and the benzocyclobutene ring Particularly preferred.

In the molecule of the polymer compound related to the present invention, the crosslinking group may be bonded directly to an aromatic hydrocarbon group or an aromatic heterocyclic group in the molecule, or may be bonded to the aromatic hydrocarbon ring through a -O- group, a -C (= O) -CH ₂ - group may be bonded to an aromatic hydrocarbon group or an aromatic heterocyclic group through a divalent group formed by connecting 1 to 30 groups in any order. Specific examples of the groups containing a crosslinkable group, that is, a group containing a crosslinkable group, via these divalent groups are shown below in the &lt; group T 'containing a crosslinkable group, but the present invention is not limited thereto.

&Lt; Group T containing a crosslinking group &gt; &gt;

[Chemical Formula 19]

[Chemical Formula 20]

The polymer compound in the present invention preferably contains a repeating unit represented by the following formula (2).

[Chemical Formula 21]

Ar ²¹ and Ar ²² each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar ²³ to Ar ²⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and T ² represents a crosslinkable group.

The aromatic hydrocarbon group which may have a substituent which may be used for Ar ²¹ , Ar ²² and Ar ²⁴ , or the aromatic heterocyclic group which may have a substituent is the same as the structure represented by Ar ^a described above. The aromatic hydrocarbon group which may have a substituent or the aromatic heterocyclic group which may have a substituent which can be used for Ar ²³ and Ar ²⁵ is the same as the structure represented by Ar ^b described above.

T ² is selected from the above-mentioned crosslinkable groups T and T '. In addition, T ² is preferably a group containing a group represented by the following formula (3).

[Chemical Formula 22]

(The benzocyclobutene ring in the formula (3) may have a substituent, and the substituents may be bonded to each other to form a ring.)

The substituent which Ar ²¹ to Ar ²⁵ may have is the same as the substituent which an aromatic hydrocarbon group or aromatic heterocyclic group represented by Ar ^a or Ar ^b described above may have.

The polymer compound in the present invention preferably contains a partial structure represented by the following formula (4).

(23)

In the formula (4), Ar ₆ and Ar ₇ each independently represent a divalent aromatic ring group which may have a substituent, Ar ₈ represents a aromatic ring group which may have a substituent, R ₈ and R ₉ each independently represent a hydrogen An alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or a aromatic ring group which may have a substituent.

R ₈ and R ₉ may combine with each other to form a ring.

p represents an integer of 1 to 5;

When a plurality of Ar ₆ to Ar ₈ , R ₈ and R ₉ are present in the formula (4), they may be the same or different.

The polymer compound in the present invention preferably contains a partial structure represented by the following formula (6).

&Lt; EMI ID =

Ar ³¹ , Ar ³³ , Ar ³⁴ and Ar ³⁵ each independently represent a bivalent aromatic hydrocarbon ring group which may have a substituent or a bivalent aromatic heterocyclic group which may have a substituent, and Ar ³² represents a substituent Or an aromatic heterocyclic group which may have a substituent.

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent and R ¹² to R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms An alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

R ¹² and R ¹³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ may combine with each other to form a ring. R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring.

l, m and n each independently represent an integer of 0 to 2;

When there are a plurality of Ar ³¹ to Ar ³⁵ or R ¹² to R ^{17 in the} formula (6), they may be the same or different.)

The divalent aromatic hydrocarbon group which may have a substituent which can be used for Ar ³¹ , Ar ³³ , Ar ³⁴ , Ar ³⁵ and Ar ₆ and Ar ₇ is the same as the divalent aromatic hydrocarbon group which can be used for the above-mentioned Ar ^a .

The aromatic hydrocarbon group which may have a substituent which can be used for Ar ³² and Ar ₈ is the same as the aromatic hydrocarbon group which can be used for Ar ^b described above.

R ¹² to R ¹⁷ and R ₈ and R ₉ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent or an aromatic group which may have a substituent, do. R ¹¹ , R ¹² to R ¹⁷ and R ₈ and R ₉ are preferably an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms in view of solubility and more preferably an alkyl group having 1 to 12 carbon atoms.

^{Ar 31, Ar 33, Ar 34} , Ar 35, Ar 6, Ar 7, R 12 ~ R 17, R 8, R 9 is a substituent which may have an aromatic hydrocarbon group or an aromatic heterocycle represented by the foregoing Ar ^a or Ar ^b A substituent which the ring group may have, or the above-mentioned crosslinkable group.

<Molecular Weight of Polymer Compound>

The weight average molecular weight (Mw) of the polymer compound in the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, and usually 2,000 or more, preferably 3,000 or more, More than 5,000.

The number average molecular weight (Mn) of the polymer compound is usually 3,000 or more, preferably 6,000 or more, and usually 1,000,000 or less, preferably 500,000 or less. If the weight average molecular weight or the number average molecular weight is lower than the lower limit of the above range, insolubility of the crosslinked layer with respect to the organic solvent is reduced and there is a possibility that lamination can not be performed, and the glass transition temperature is lowered and the heat resistance is likely to be impaired . If the upper limit of the above range is exceeded, it is not dissolved in the organic solvent even before crosslinking, and a flat film may not be obtained.

The dispersion degree (Mw / Mn) of the polymer compound in the present invention is usually 3.5 or less, preferably 2.5 or less, and more preferably 2.0 or less. If the degree of dispersion of the polymer compound exceeds the upper limit of the above range, there is a possibility that purification becomes difficult, the solubility in an organic solvent is lowered, and the charge transporting ability is lowered. The dispersion degree is ideally 1.0.

Typically, this weight average molecular weight is determined by SEC (size exclusion chromatography) measurement. In the SEC measurement, the elution time is shorter for a higher molecular weight component and elongation time is longer for a lower molecular weight component. However, by using a calibration curve calculated from the elution time of polystyrene (standard sample) already known in molecular weight, Whereby the weight average molecular weight is calculated.

Hereinafter, a method of heating the conductive thin film precursor containing the above-described polymer compound will be described.

The conductive thin film precursor is prepared by mixing a conductive thin film-forming material such as the above-described polymer compound and, if necessary, other components with a solvent capable of dissolving or dispersing.

The solvent contained in the conductive thin film precursor is not particularly limited, but is usually a solvent which dissolves the above polymer compound in an amount of usually not less than 0.1% by weight, preferably not less than 0.5% by weight, more preferably not less than 1.0% by weight.

The boiling point of the solvent is usually 110 ° C or higher, preferably 140 ° C or higher, more preferably 180 ° C or higher, particularly preferably 200 ° C or higher, usually 400 ° C or lower, and most preferably 300 ° C or lower. If the boiling point of the solvent is too low, the drying speed is too fast and the film quality may deteriorate. If the boiling point of the solvent is too high, it is necessary to raise the temperature of the drying step, which may adversely affect other layers or substrates.

The solvent contained in the conductive thin film precursor may be an ester solvent, an aromatic hydrocarbon solvent, an ether solvent, a halohydric organic solvent, an amide solvent, or the like, and may be an ester solvent, Aromatic hydrocarbon solvents and ether solvents are preferable because of their high solubility and low adverse effects of residual solvents.

Examples of the ester solvents include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate, phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, And the like.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene And methylnaphthalene.

Examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3- Aromatic ethers such as dimethoxybenzene, anisole, phenetole, 2-methoxy toluene, 3-methoxy toluene, 4-methoxy toluene, 2,3-dimethyl anisole and 2,4- Based solvent and the like.

Examples of the halogenated organic solvent include 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene.

Examples of the amide solvent include N, N-dimethylformamide and N, N-dimethylacetamide.

In addition to these, dimethylsulfoxide and the like can also be used.

These solvents may be used alone or in combination of two or more in any combination.

The amount of the solvent contained in the conductive thin film precursor is generally at least 10% by weight, preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight and usually not more than 99.99% to be.

The amount of the conductive thin film-forming material contained in the conductive thin film precursor is preferably as large as possible because the viscosity of the composition is high, but is preferably small as far as solubility is concerned. Specifically, the amount of the conductive thin film-forming material contained in the conductive thin film precursor is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, Preferably 50 wt% or less, more preferably 40 wt% or less, and even more preferably 20 wt% or less. The composition for forming an electroconductive thin film may contain two or more electroconductive thin film forming materials. In this case, it is preferable that the total of two or more electroconductive thin film forming materials falls within the above range.

(Heating condition)

The heating of the conductive thin film precursor by infrared rays is usually a lower limit value of the substrate temperature in infrared irradiation of 150 DEG C or higher, preferably 160 DEG C or higher, more preferably 170 DEG C or higher, and even more preferably 180 DEG C or higher. The upper limit value is usually 300 占 폚 or lower, preferably 290 占 폚 or lower, more preferably 280 占 폚 or lower, still more preferably 270 占 폚 or lower.

When the temperature of the substrate is within the above-mentioned range, if the conductive thin film is not heated more than necessary and the conductive thin film is a material which is not heated well by infrared rays, heat can be given to the conductive thin film from the substrate.

Further, in the above-described range, when the conductive thin film is formed by a coating method, the solvent can be removed, the density in the layer can be increased, the adhesion between the layers can be enhanced and the characteristics of the conductive thin film can be improved have.

The lower limit value of the holding time in the temperature range described above is usually 5 seconds or more, preferably 20 seconds or more, more preferably 30 seconds or more. The upper limit value is usually 30 minutes or less, preferably 25 minutes or less, more preferably 20 minutes or less.

With this range, when the conductive thin film is not heated more than necessary and the conductive thin film is a material which is not heated well by infrared rays, heat can be given to the conductive thin film from the substrate.

Further, in the above-mentioned range, when the conductive thin film is formed by coating, the solvent can be removed, the uniformity and the film strength in the layer can be increased, the adhesion between the layers can be enhanced, .

In the above-mentioned range, when the conductive polymer thin film according to the present invention has a crosslinkable group, it is preferable that the polymeric compound according to the present invention has a crosslinkable group and can be crosslinked and insolubilized by the crosslinkable group.

The time for which the temperature of the substrate in the infrared irradiation is maintained at a constant temperature in the temperature range of 150 DEG C or higher and 300 DEG C or lower is usually 20 seconds or more, preferably 30 seconds or more, more preferably 1 minute Or more. The upper limit value is usually 15 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less.

Within this range, formation of a metastable state in a state in which characteristics required by the conductive thin film can not be obtained is prevented, and the conductive thin film can be stably formed. Concretely, it is possible to prevent the component of the film from interfering with phase separation and from increasing the roughness of the surface structure based on phase separation.

The term "maintaining at a constant temperature" means that the temperature is maintained within a range of ± 5 ° C.

The rate of temperature rise of the substrate in the conductive thin film laminate is usually 10 ° C / min or more, preferably 20 ° C / min or more, and more preferably 30 ° C / min or more. The upper limit value is usually 250 占 폚 / min or less, preferably 200 占 폚 / min or less, and more preferably 150 占 폚 / min or less.

The rate of temperature rise shall be measured for 30 seconds.

By setting the heating rate in this range, it is possible to effectively suppress the shrinkage of the conductive thin film and to effectively heat the conductive thin film, thereby improving the productivity.

The infrared ray transmittance of the substrate has a minimum value of the transmittance in the wavelength range of 2000 to 3300 nm and the product of the wavelength in the minimum value and the peak wavelength of the infrared heater is set to 150 ° C or higher (? / T) divided by the holding time (t) at the time t1 satisfies the relationship of the following formula (7).

0.002?? / T (? ² / s)? 0.2 (7)

The lower limit value of? / t is usually 0.002 占 퐉 ² / s or more, preferably 0.005 占 퐉 ² / s or more, more preferably 0.01 占 퐉 ² / s or more, and still more preferably 0.02 占 퐉 ² / s or more. The upper limit value is usually 0.2 m ² / s or less, preferably 0.1 m ² / s or less, more preferably 0.05 m ² / s or less, and still more preferably 0.04 m ² / s or less.

When? / t is in this range, the substrate can be removed from the heat of the conductive thin film that is excessively heated by infrared rays, and breakdown of the conductive thin film can be suppressed. Further, even when the conductive thin film is weakly heated by infrared rays, the substrate is appropriately heated and the thin film is heated with the heat. That is, when? / T is in this range, the conductive thin film can be appropriately heated and the performance of the conductive thin film can be enhanced.

This parameter? / T will be described below. As described above, the parameter? Is in inverse proportion to the ease with which the substrate is heated. That is, when? Is small, the substrate tends to be heated. To heat the conductive thin film, the holding time t may be short. When? Is large, the substrate is not heated well and the time t is long.

Therefore, by dividing? By t, suitable heating conditions can be set in the production of the conductive thin film laminate according to the present invention, and the range is as described above.

(Relative to the film thickness)

Here, when the conductive thin film containing the polymer compound contains a crosslinking group in the polymer compound as the conductive thin film precursor, the thick film is liable to be insolubilized. The thick film means that the thickness of the formed film is usually 50 nm or more, preferably 60 nm or more, more preferably 100 nm or more, further preferably 120 nm or more, usually 1 占 퐉 or less, preferably 800 nm or less , And more preferably 600 nm or less.

When the conductive thin film precursor is heated by infrared rays, molecules constituting the polymer compound are vibrated by infrared induction heating. However, the hole transporting material on the substrate or the transparent electrode is bound to the molecular motion by the adsorption of molecules on the surface thereof, so that insolubilization such as crosslinking reaction does not proceed well. On the other hand, when the conductive thin film has a thickness of 50 nm or more, sufficient molecular motion can be carried out, and the probability of collision between the crosslinking groups can be increased and the crosslinking reaction can be promoted. Further, if the film thickness of the conductive thin film is 50 nm or more, the heat generated by infrared induction heating can contribute to the promotion of the crosslinking reaction of the polymer compound, without excessively depriving the substrate of heat due to heat transfer.

Another advantage of using the conductive thin film as a thick film is to increase the covering ratio of the foreign substance as a leak source. Further, it is possible to increase the degree of freedom of optical design of the organic electroluminescent device based on interference of light.

On the other hand, by setting the film thickness of the conductive thin film to 1 m or less, the drying time of the solvent can be shortened, and the amount of the polymer compound used can be limited, and the cost can be suppressed.

When heating the conductive thin film having a film thickness of 50 nm or more, the lower limit value of the substrate temperature in infrared heating is usually 70 ° C or higher, preferably 100 ° C or higher, more preferably 120 ° C or higher, Lt; / RTI &gt; The upper limit value is usually 300 占 폚 or lower, preferably 290 占 폚 or lower, more preferably 280 占 폚 or lower, still more preferably 270 占 폚 or lower.

When the temperature of the substrate is within the above-mentioned range, heat can be given to the conductive thin film from the substrate when the conductive thin film is not heated more than necessary and is not heated well by infrared rays.

Further, in the above-described range, when the electroconductive thin film is formed, the solvent can be removed, the density in the layer can be increased, the adhesion between the layers can be improved, and the characteristics of the electroconductive thin film can be improved Can be improved.

Also, the lower limit value of the holding time in the above-described temperature range is usually 5 seconds or more, preferably 20 seconds or more, more preferably 30 seconds or more. The upper limit value is usually 30 minutes or less, preferably 25 minutes or less, more preferably 20 minutes or less.

With this range, heat can be given to the conductive thin film from the substrate when the conductive thin film is not heated more than necessary and is not heated well by infrared rays.

Further, in the above-mentioned range, when the conductive thin film is formed by coating, the solvent can be removed, the uniformity and the film strength in the layer can be increased, the adhesion between the layers can be enhanced, .

In the above-mentioned range, when the conductive polymer thin film according to the present invention has a crosslinkable group, it is preferable that the crosslinkable group is crosslinked and insolubilized by the crosslinkable group.

The lower limit of the time at which the temperature of the substrate is maintained at a constant temperature in the temperature range of 70 ° C or higher and 300 ° C or lower is usually 20 seconds or more, preferably 30 seconds or more, more preferably 1 minute or more. The upper limit value is usually 15 minutes or less, preferably 8 minutes or less, more preferably 5 minutes or less.

Within this range, formation of a metastable state in a state in which characteristics required by the conductive thin film can not be obtained is prevented, and the hole transporting material layer can be stably formed. Concretely, it is possible to prevent the component of the film from interfering with phase separation and from increasing the roughness of the surface structure based on phase separation.

The term "maintaining at a constant temperature" means that the temperature is maintained within a range of ± 5 ° C.

The rate of temperature rise of the substrate is usually 10 ° C / min or more, preferably 20 ° C / min or more, and more preferably 30 ° C / min or more. The upper limit value is usually 250 占 폚 / min or less, preferably 200 占 폚 / min or less, and more preferably 150 占 폚 / min or less.

The rate of temperature rise shall be measured for 30 seconds.

By setting the heating rate in this range, the conductive thin film can be effectively heated without sharply shrinking, and productivity can be increased.

The infrared ray transmittance of the substrate has a minimum value of the transmittance in a wavelength range of 2000 to 3300 nm and the product of the wavelength in the minimum value and the peak wavelength of the infrared ray heater is set to be longer than the time (t) , The lower limit value thereof is usually not less than 0.002 탆 ² / s, preferably not less than 0.005 탆 ² / s, more preferably not less than 0.01 탆 ² / s, more preferably not less than 0.02 탆 ² / s.

The upper limit value is usually 0.2 μm ² / s or less, preferably 0.15 μm ² / s or less, more preferably 0.10 μm ² / s or less, and still more preferably 0.08 μm ² / s or less.

When? / t is in this range, the substrate can be removed from the heat of the conductive thin film that is excessively heated by infrared rays, and breakdown of the conductive thin film can be suppressed. In addition, even when the conductive thin film is weakly heated by infrared rays, the substrate is appropriately heated, and the conductive thin film is heated with the heat. That is, when? / T is in this range, the conductive thin film can be appropriately heated and the performance of the conductive thin film can be enhanced.

(Film forming method)

Examples of the application method of the conductive thin film precursor composition in the present invention include a spin coating method, a dip coating method, a die coating method, a bar coating method, a blade coating method, a roll coating method, a spray coating method, A coating method, an ink jet method, a nozzle printing method, a screen printing method, a gravure printing method, and a flexo printing method.

The temperature at the time of film formation is preferably 10 ° C or higher, more preferably 50 ° C or lower in the point that film defect due to crystals formed in the composition hardly occurs. The relative humidity at the time of film formation is not limited so long as it does not significantly impair the effect of the present invention, but is usually not less than 0.01 ppm, usually not more than 80%.

Prior to the step of heating with infrared rays according to the present invention, a dried film may be obtained by drying the coated film by heating, vacuum drying or the like. Examples of the heating means include a hot plate and a clean oven. Specifically, for example, a dried film can be obtained by heating the substrate on which a coating film has been formed by placing it on a hot plate or heating it in an oven. In the reduced-pressure drying, the substrate on which the coating film is formed is placed in a decompression apparatus and decompressed to obtain a dried film. Since the surface of the conductive thin film after infrared heating is more flat, it is preferable to dry the coating film to form a dried film before the infrared ray heating process according to the present invention.

According to the production method of the present invention, a conductive thin film laminate can be produced without giving more heat to the conductive thin film than necessary. Generally, polymeric materials typically form a coiled state in solution. However, when the polymer is heated to a temperature higher than the glass transition temperature or the softening temperature of the polymer material and the solvent is cast, it is slightly shrunk. When such a thin film is heated for a sufficient time, the voids are diffused and become a random state intertwined with each other. In the present invention, since the heating time is shortened, it is considered that such a state of failure is maintained. A method for determining the structure can be appropriately selected. However, in order to measure the structure of the thin film layer, measurement by fine angle X-ray scattering (GI-SAXS) is preferable. This structure is usually 1 to 50 nm, preferably 2 to 40 nm, more preferably 3 to 30 nm. If it is outside this range, there is a possibility that a sufficient conductive path can not be obtained.

The conductive thin film containing the polymer compound thus formed is preferably formed as a hole injecting layer or a hole transporting layer in an organic electroluminescent device to be described later. Next, an organic electroluminescent device will be described as a suitable example of the conductive thin film laminate.

6. Organic electroluminescent device

The organic electroluminescent device is an organic electroluminescent device having an anode, a cathode, and at least one organic layer as a conductive thin film therebetween. 1 is a schematic view of a cross section showing a structural example suitable for an organic electroluminescent device. In Fig. 1, reference numeral 1 denotes a substrate, reference numeral 2 denotes an anode, reference numeral 3 denotes a hole injecting layer, reference numeral 4 denotes a hole transporting layer, , Numeral 6 denotes a hole blocking layer, numeral 7 denotes an electron transporting layer, numeral 8 denotes an electron injecting layer, and numeral 9 denotes a cathode. In Fig. 1, the layer corresponding to the conductive thin film layer of the present invention is indicated by 3 to 8. It is preferable that at least one of these conductive thin film layers is formed by a wet film forming method and that a layer is formed by infrared ray heating. Next, the light emitting layer will be described as a conductive thin film.

[Light Emitting Layer]

(Method of forming light emitting layer)

The light emitting layer is formed by applying a light emitting layer composition containing a light emitting material and a solvent, and performing firing.

(Luminescent material)

As the light emitting material, known materials can be applied. For example, it may be a fluorescent light emitting material or a phosphorescent light emitting material. Details will be described later.

(Light Emitting Layer Composition)

The light emitting layer composition includes at least a light emitting material and a solvent. As the solvent, the same solvent as the solvent contained in the composition for forming a conductive thin film may be used. The light emitting material contained in the composition is usually contained in an amount of 0.01 wt% or more, preferably 0.05 wt% or more, more preferably 0.1 wt% or more. The light emitting material is preferably contained in an amount of 35% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. When two or more kinds of light emitting materials are used in combination, it is preferable that the content of these total materials is included in the above range.

The boiling point of the solvent is usually 75 ° C or higher, preferably 100 ° C or higher, more preferably 110 ° C or higher, further preferably 120 ° C or higher, and usually 350 ° C or lower, preferably 280 ° C or lower Preferably 275 DEG C or lower, more preferably 260 DEG C or lower.

If it is at least the lower limit value, there is no possibility that the coating film becomes uneven due to drying before heating and firing of the light emitting layer. If the upper limit is not exceeded, the solvent can be sufficiently removed, and desired characteristics of the organic electroluminescence layer can be obtained. In addition, solvent removal can be achieved in a short time, and productivity is improved. As the method of applying the light emitting layer composition, a method of applying the composition for forming a conductive thin film described above can be used.

(Infrared heating)

The light emitting layer composition applied as described above is baked by infrared heating. As the infrared heating conditions, the lower limit temperature of the substrate is usually 70 ° C or higher, preferably 75 ° C or higher, more preferably 80 ° C or higher, and the upper limit temperature is usually 150 ° C or lower, preferably 140 ° C or lower Preferably 130 DEG C or less. In this temperature range, it is usually at least 5 seconds, preferably at least 10 seconds, more preferably at least 20 seconds, particularly preferably at least 30 seconds, usually at most 20 minutes, preferably at most 15 minutes, 10 minutes or less, and more preferably 8 minutes or less.

When the above-mentioned light emitting layer composition is applied to the previously formed hole injection layer or the hole transporting layer, the solvent is sufficiently volatilized and the solvent is not left, Characteristics can be realized.

If the temperature is lower than the upper limit of the holding time, there is no risk of destroying the light emitting layer due to the absorption of infrared rays, and thus the device characteristics can be maintained.

Further, it is preferable that the time for which the temperature of the substrate is kept constant in the temperature range is 20 seconds or more, preferably 30 seconds or more, more preferably 1 minute or more, and usually 10 minutes or less, 8 minutes or less, and more preferably 5 minutes or less.

If the temperature is kept below the upper limit time, desired characteristics can be exhibited without forming a metastable state. Usually, the light emitting layer is formed of a mixture of a host and a dopant, and therefore, if the film is maintained at a normal temperature for a long time, the light emitting layer component may cause phase separation in the film or the surface roughness of the surface structure may increase. Further, if the temperature is maintained at the above-mentioned lower limit time or longer, the state of the light emitting layer is controlled and light emission can be reproduced.

Here, the term &quot; constant temperature &quot; refers to a state in which the temperature is maintained within a range of 占 5 占 폚.

The heating rate of the substrate is usually 10 ° C / min or more, preferably 20 ° C / min or more, more preferably 30 ° C / min or more, usually 250 ° C / min or less, preferably 200 ° C / More preferably not higher than 150 ° C / min.

If the heating rate is lower than the heating rate, there is no rapid temperature rise, and the light emitting layer is not destroyed. On the other hand, if the heating rate is higher than the heating rate, it does not take much time to reach the temperature for achieving the required characteristics, which is preferable from the viewpoint of productivity. The heating rate is measured for 30 seconds.

Typically, the light emitting layer contains a host and a dopant, and the amount ratio thereof needs precise control. In the vapor deposition method, it is difficult to keep the respective deposition rates constant over a long period of time, and the error ratio is large. In the wet film forming method, since the ink containing the light emitting material and the solvent is precisely adjusted by weighing the material in advance, it is an effective method in that there is no change in the amount ratio and deviation of the element can be suppressed.

In addition, in the vapor deposition method, once the material charged into the evaporation source of the film-forming apparatus is continuously heated for a long time, the time becomes longer as the apparatus becomes larger, and the problem of material deterioration becomes present.

In the wet film forming method, since the material is heated only during drying, the material put in the film forming apparatus stably exists without deterioration over a long period of time, and the quality of the device can be kept constant. Further, it can be a useful method in that heating time can be shortened by heating using the infrared ray of the present invention at the time of heating. Further, by using infrared rays as the heating means, firing in a relatively short time is possible, compared with the case of using a hot air furnace or a hot plate. Therefore, the effect of gas in a firing atmosphere such as oxygen and moisture and the influence of dust are minimized This can be an advantage.

It is preferable that at least one organic layer, specifically, a hole injection layer and a hole transport layer are baked by infrared rays at a temperature higher than the baking temperature of the light emitting layer before forming the light emitting layer.

This is because there is a possibility that degassing occurs from the hole injecting layer or the hole transporting layer by heating of the light emitting layer and the light emitting layer is contaminated. Further, when the hole injection layer or the hole transport layer is heated by a method other than infrared ray, a skin layer may be formed on the surface, and the residual solvent may be deposited on the hole injection layer or the hole transport layer. This is because molecular vibrations due to infrared heating occur, the residual solvent is easily removed, and the skin layer is not formed well due to molecular vibration or the solvent is easily removed even if it is formed.

(Relationship between substrate and infrared rays)

The product (a) of the wavelength at the minimum value of the types of the usable heater, the minimum infrared ray transmittance of the substrate, the infrared ray transmittance, the peak wavelength of the infrared ray heater and the infrared ray transmittance of the substrate and the peak wavelength of the infrared ray heater during the infrared ray heating Described infrared ray heating of the conductive thin film.

It is also preferable that the infrared transmittance of the substrate has a minimum value of the transmittance in the wavelength range of 2000 to 3300 nm and the product of the wavelength in the minimum value and the peak wavelength of the infrared heater is 70 ° C or more (? / T) divided by the holding time (t) at 150 占 폚 or less satisfies the relationship of the following formula (8).

0.003?? / T (? ² / s)? 0.5 (8)

The lower limit value of? / t is usually 0.003 占 퐉 ² / s or more, preferably 0.004 占 퐉 ² / s or more, more preferably 0.005 占 퐉 ² / s or more, and still more preferably 0.008 占 퐉 ² / s or more. The upper limit value is usually 0.5 μm ² / s or less, preferably 0.4 μm ² / s or less, more preferably 0.3 μm ² / s or less, particularly preferably 0.2 μm ² / s or less.

When? / t is within this range, the substrate can be removed from the heat of the light-emitting layer which is excessively heated by infrared rays, and breakdown of the light-emitting layer can be suppressed. Further, even when the light-emitting layer is weakly heated by infrared rays, the substrate is appropriately heated to heat the light-emitting layer with the heat. That is, when? / T is in this range, the light emitting layer can be appropriately heated and the performance of the organic electroluminescent device can be enhanced.

(Relation between heating temperature and solvent)

When the light emitting layer is formed by coating, the difference (? T = t1 - t2) between the boiling point (t1) of the solvent used in the light emitting layer composition and the maximum temperature (t2) of the substrate temperature is usually 5 ° C or more, More preferably not less than 50 ° C, more preferably not less than 100 ° C, particularly preferably not less than 120 ° C, and usually not more than 230 ° C, preferably not more than 200 ° C, more preferably not more than 190 ° C Lt; RTI ID = 0.0 &gt; 185 C, &lt; / RTI &gt;

In the case of heating with infrared rays, if the upper limit is not exceeded, there is no fear that the light emitting layer which is a thin film is destroyed due to the rapid evaporation or boiling of the solvent by infrared electromagnetic induction heating. If the lower limit is more than the lower limit, the solvent can be sufficiently removed and desired characteristics of the organic electroluminescence layer can be obtained. In addition, removal of the solvent can be achieved in a short time, and productivity is improved.

The film thickness of the light emitting layer is usually 3 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

(Luminescent material)

Examples of the fluorescent light emitting material (blue fluorescent pigment) that emits blue light include a fluorescent material such as naphthalene, chrysene, perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) .

Examples of fluorescent dyes (green fluorescent dyes) that give green luminescence include quinacridone derivatives, coumarin derivatives, and aluminum complexes such as Al (C ₉ H ₆ NO) ₃ .

Examples of a fluorescent light-emitting material (yellow fluorescent pigment) that imparts yellow light emission include rubrene, ferrimidone derivatives, and the like.

Examples of the fluorescent light-emitting material (red fluorescent pigment) for imparting red light emission include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) A rhodamine derivative, a benzothioxantine derivative, and azabenzothiazane.

Specific examples of the phosphorescent material include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethylpalladium porphyrin, octaphenylpalladium porphyrin and the like.

Examples of the polymer light emitting material include poly (9,9-dioctylfluorene-2,7-diyl), poly [(9,9-dioctylfluorene-2,7-diyl) 4 '- (N- (4-sec-butylphenyl)) diphenylamine)], poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4- (2,1'-3} -triazole)] and poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] And polyphenylene vinylene-based materials.

In addition, the above-described polymer compound may be used as a light emitting material.

The molecular weight of the compound used as the light emitting material is not particularly limited so long as it does not significantly impair the effect of the present invention, but is usually 10,000 or less, preferably 5,000 or less, more preferably 4,000 or less, further preferably 3,000 or less, But is usually in the range of 100 or more, preferably 200 or more, more preferably 300 or more, and further preferably 400 or more. If the molecular weight of the light emitting material is too small, the heat resistance may remarkably decrease, gas may be generated, film quality may be lowered when the film is formed, or morphology of the organic electroluminescence device may be caused by migration or the like Or the like. On the other hand, if the molecular weight of the light-emitting material is too large, purification of the organic compound tends to be difficult, or time tends to be required in dissolving in a solvent.

The above-described luminescent materials may be used either singly or in combination of two or more in any combination and ratio.

From the viewpoint of internal quantum efficiency, it is preferably a phosphorescent material. Examples of the phosphorescent material include a metal selected from Groups 7 to 11 of a long period type periodic table (hereinafter, unless otherwise specified, the term "periodic table" refers to a long period type periodic table) A Werner complex or an organometallic complex compound contained as a central metal. Further, the metal complex compound having Ir or the like as a heavy element is more preferable because it has excellent heat resistance.

Particularly, the phosphorescent organic metal complex of the phosphorescent material is preferably a compound represented by the following formula (III) or (IV).

ML _{( qj)} L ' _j (III)

(Wherein M represents a metal, q represents a valence of the metal, L and L 'represent two-position ligands, j represents 0, 1 or 2. L or L ', A plurality of L or a plurality of L' may be the same or different from each other.)

(25)

(Formula (IV) of, M ⁷ represents a metal, T represents a carbon atom or a nitrogen atom. R ⁹² ~ R ⁹⁵ represents a substituent, independently. However, when t is a nitrogen atom, R ^94, and There is no R ^95. )

Hereinafter, the compound represented by formula (III) will be described first.

In the formula (III), M is a metal selected from Groups 7 to 11 of the periodic table, preferably ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold. Preferably iridium or platinum, and most preferably iridium in terms of high stability and high luminous efficiency.

In the formula (III), the two-position ligand L represents a ligand having the following partial structure.

(26)

In the partial structure of L, ring A1 represents a aromatic ring group which may have a substituent. The aromatic ring group in the present invention may be an aromatic hydrocarbon ring group or an aromatic heterocyclic ring group.

Examples of the aromatic hydrocarbon ring group include a monocyclic or bicyclic condensed ring of 5 or 6 atomic rings having one free valence.

Specific examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, Triphenylene ring, acenaphthene ring, fluoranthene ring and fluorene ring.

The aromatic heterocyclic group includes a monocyclic or bicyclic condensed ring of 5 or 6 atomic rings having one free valence.

Specific examples include compounds having one free valence group such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisothiazole ring, benzoisothiazole ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinine ring A heterocyclic ring, a zolene ring, a quinazolinone ring, and an azulene ring.

In the partial structure of L, the ring A2 may have a substituent and represents a nitrogen-containing aromatic heterocyclic group.

Examples of the nitrogen-containing aromatic heterocyclic group include monocyclic or bicyclic condensed rings of 5 or 6-membered rings each having one free valence.

Specific examples include compounds having one free valence such as a pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole A thiophenol ring, a thienopyran ring, a benzoisooxazole ring, a benzoisothiazole ring, a benzoimidazole ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, A quinoline ring, an isoquinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, and a quinazolinone ring.

Examples of the substituent which Ring A1 or Ring A2 may have respectively include a halogen atom, an alkyl group, an alkenyl group, an alkoxycarbonyl group, an alkoxy group, an aralkyl group, an aryloxy group, a dialkylamino group, a diarylamino group, A haloalkyl group, a cyano group, and an aromatic hydrocarbon ring group. The ring A1 may be a nitrogen-containing aromatic heterocyclic group, and the ring A2 may have an aromatic hydrocarbon ring group as a substituent.

In the formula (III), the two-position ligand L 'represents a ligand having the following partial structure. In the following formulas, &quot; Ph &quot; represents a phenyl group.

(27)

Among them, L 'is preferably a ligand exemplified below from the viewpoint of stability of the complex.

(28)

As the compound represented by the formula (III), compounds represented by the following formulas (IIIa), (IIIb) and (IIIc) are more preferable.

[Chemical Formula 29]

(In the formula (IIIa), M ⁴ represents a metal the same as M, w represents a valence of the metal, ring A 1 represents an aromatic hydrocarbon ring group which may have a substituent, ring A 2 represents a nitrogen atom which may have a substituent A plurality of ring A1 or ring A2 may be the same or different.) When ring A1 or ring A2 has a plurality of rings, ring A1 or ring A2 may be the same or different.

(30)

(Wherein (IIIb), also M ⁵ is that represents the same metal as M, w-1 represents the valence of the metal, ring A1 represents an aromatic ring which may have a substituent, and ring A2 has may have a substituent A plurality of ring A1 or ring A2 may be the same or different.) When ring A1 or ring A2 has a plurality of rings, ring A1 or ring A2 may be the same or different.

(31)

(In the formula (IIIc), M ⁶ represents a metal the same as M, w represents a valence of the metal, j represents 0, 1 or 2, and the ring A1 and the ring A1 'each independently have a substituent And the ring A2 and the ring A2 'each independently represent a nitrogen-containing aromatic heterocyclic group which may have a substituent. When there are a plurality of rings A1, a ring A1', a ring A2 or a ring A2 ', a plurality of rings A1, the ring A1 ', the ring A2 or the ring A2' may be the same or different.

In the above formulas (IIIa) to (IIIc), preferred examples of the aromatic ring group of ring A1 and ring A1 'are phenyl group, biphenyl group, naphthyl group, anthryl group, thienyl group, furyl group, benzothienyl group, A furyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, and a carbazolyl group.

In the formulas (IIIa) to (IIIc), preferred examples of the nitrogen-containing aromatic heterocyclic group of the ring A2 and the ring A2 'include a pyridyl group, a pyrimidyl group, a pyrazyl group, a triazole group, a benzothiazole group, , A benzoimidazole group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, and a phenanthridyl group.

Examples of the substituent which the ring A1 of the formula (IIIa) to (IIIc) and the nitrogen ring aromatic heterocyclic group of the ring A2 'of the aromatic ring group of the ring A1', the ring A2 and the ring A2 'may have include a halogen atom, An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a di An alkylamino group, a diarylamino group having 8 to 24 carbon atoms, an aromatic hydrocarbon ring group having 5 or 6 ring atoms, or a 2 to 4 condensed ring, a carbazolyl group, an acyl group, a haloalkyl group and a cyano group. A diarylamino group having 8 to 24 carbon atoms, a monocyclic or bicyclic condensed aromatic hydrocarbon ring group or a carbazolyl group having 5 or 6 ring atoms may further have a substituent at the aryl moiety constituting the group, Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, a 5 to 6-membered ring optionally substituted with an alkyl group having 1 to 12 carbon atoms, And an aromatic hydrocarbon ring group.

These substituents may be connected to each other to form a ring. As a specific example, a substituent group of the ring A1 may be bonded to a substituent group of the ring A2, or a substituent group of the ring A1 'may be combined with a substituent group of the ring A2' to form a single condensed ring. Examples of such a condensed ring include a 7,8-benzoquinoline group and the like.

Among them, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, 5 or 6 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, A halogen atom, a haloalkyl group, a diarylamino group and a carbazolyl group, more preferably an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms An aralkyl group having 1 to 24 carbon atoms, an aromatic hydrocarbon ring group, a diarylamino group or a carbazolyl group which is a monocyclic or bicyclic condensed ring of a 5 or 6-membered ring, a monocycle of a 5 or 6-membered ring, The aromatic hydrocarbon ring group, diarylamino group, and carbazolyl group which are condensed to four carbons may further have a substituent at the aryl moiety constituting the group, and examples of the substituent include groups having 1 to 12 carbon atoms An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aralkyl group having 1 to 24 carbon atoms, an aromatic hydrocarbon ring group having 5 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms or a 2 to 4 condensed ring .

A preferable example of M ⁴ to M ⁶ in formulas (IIIa) to (IIIc) is the same as M.

Specific examples of the organometallic complexes represented by the above formulas (III) and (IIIa) to (IIIc) are shown below, but are not limited to the following compounds.

(32)

(33)

(34)

(35)

Among the organometallic complexes represented by the above formula (III), particularly preferred are ligands of 2-arylpyridine as ligands L and / or L ', that is, 2-arylpyridine, an arbitrary substituent bonded thereto, Are condensed with each other.

The compounds described in International Publication WO 2005/019373 can also be used as a light emitting material.

Next, the compound represented by the formula (IV) will be described.

In the formula (IV), M ⁷ represents a metal. Specific examples of the metal selected from Groups 7 to 11 of the Periodic Table include metals and the like. Roneun M ^7, In particular, preferably, ruthenium, rhodium, palladium, silver, rhenium, can be exemplified by osmium, iridium, platinum or gold, may be particularly preferably a divalent metal of the platinum and palladium.

In the formula (IV), R ⁹² and R ⁹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, , Aralkylamino group, haloalkyl group, hydroxyl group, aryloxy group and aromatic ring group.

When T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent the same substituent as those exemplified as R ⁹² and R ⁹³ . When T is a nitrogen atom, R ⁹⁴ and R ⁹⁵ are absent.

R ⁹² to R ⁹⁵ may further have a substituent. When it has a substituent, there is no particular limitation on its kind, and any group may be used as a substituent.

In addition, any two or more of R ⁹² to R ^{95 may} be connected to each other to form a ring.

Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by the formula (IV) are shown below, but are not limited to the following examples. In the following formulas, "Me" represents a methyl group and "Et" represents an ethyl group.

(36)

These light emitting materials may be used singly or two or more kinds may be used in any combination and ratio. In the present invention, five or more kinds of charge transporting materials and light emitting materials are contained in the light emitting layer.

<Molecular Weight>

The molecular weight of the light-emitting material in the present invention is arbitrary as long as it does not significantly impair the effect of the present invention. The molecular weight of the light emitting material in the present invention is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, particularly preferably 3,000 or less. The molecular weight of the light-emitting material in the present invention is usually 100 or more, preferably 200 or more, more preferably 300 or more, and further preferably 400 or more.

The molecular weight of the luminescent material is high because of its high glass transition temperature, melting point, decomposition temperature and the like, excellent luminescent layer material and heat resistance of the formed luminescent layer, and low film quality caused by gas generation, recrystallization, It is preferable that the increase in the concentration of the impurity accompanied with the increase of the concentration of the impurities is small. On the other hand, the molecular weight of the light emitting material is preferably small in view of easy purification of the organic compound and easy dissolution in a solvent.

The light emitting layer preferably contains a host material such as a hole transporting material and an electron transporting material in addition to the above-described light emitting material.

Examples of the low molecular weight hole transporting material include two or more tertiary amines represented by 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl and two or more condensed aromatic Aromatic amine compounds having a starburst structure such as aromatic diamines whose rings are substituted with nitrogen atoms (JP-A-5-234681), 4,4 ', 4 "-tris (1-naphthylphenylamino) (Chemical Communications, 1996, pp. 2175), 2,2 ', 7,7 &lt; RTI ID = 0.0 &gt; And spiro compounds such as' -tetrakis- (diphenylamino) -9,9'-spirobifluorene (Synthetic Metals, 1997, Vol. 91, pp. 209).

Examples of the low molecular weight electron transporting material include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND), 2,5-bis (6 ' -Bipyridyl)) - 1,1-dimethyl-3,4-diphenylsilyl (PyPySPyPy), or basophenanthroline (BPhen) or 2,9- (P-tert-butylphenyl) -1,3,4-oxadiazole (tBu-PBD), 4 (4-biphenylylene) , 4'-bis (9-carbazole) -biphenyl (CBP), 9,10-di- (2-naphthyl) anthracene (ADN).

Specific examples of other host materials include those described in JP-A-2007-067383, JP-A-2007-88433, and JP-A-2007-110093.

&Lt; General Formula (A) &gt;

(37)

(A-1), (A-2) and (A-3), and Xa ¹ , Xa ² , Ya ¹ , Ya ² , Za ¹ and Za ² each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent, and Xa ³ , Ya ³ and Za ³ are each independently Represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent.

(38)

&Lt; General Formula (E) &gt;

[Chemical Formula 39]

(In the general formula (E), Xe ¹ , Xe ² , Ye ¹ , Ye ² , Ze ¹ and Ze ² each independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, And Xe ³ , Ye ³ and Ze ³ each independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 3 to 30 carbon atoms, which may have a substituent, An aromatic heterocyclic group having 1 to 30 carbon atoms.

Xa ¹ , Xa ² , Ya ¹ , Ya ² , Za ¹ and Za ² in the general formula (A), Xe ¹ , Xe ² , Ye ¹ , Ye ² and Ze ^{1 in} the general formula (E) And Ze ² each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent. Among them, an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, is preferable from the standpoint of stability of the compound.

As the aromatic hydrocarbon ring which forms an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocycle of 6-membered rings or a condensed ring of 2 to 5 is preferable. Specific examples thereof include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings and fluoranthene rings. Among them, benzene ring is preferable from the viewpoint of stability and solubility of the compound.

At least one of Xa ¹ , Xa ² , Ya ¹ , Ya ² , Za ¹ and Za ² in the general formula (A) is preferably a 1,2-phenylene group or a 1,3-phenylene group, More preferably one of Xa ¹ and Xa ² , at least one of Ya ¹ and Ya ² , or at least two of Za ¹ and Za ² is a 1,2-phenylene group or a 3-phenylene group, Most preferably a 1,3-phenylene group, and most preferably a 1,3-phenylene group. Phenylene group or 1,3-phenylene group, the stereostructure of the molecular structure is increased, the solubility in a solvent is increased, and the non-conjugative bond is increased, so that the energy gap of the molecule is increased. In particular, Triplet energy is high, it is preferable as a HOST material of a phosphorescent material. Further, the 1,3-phenylene group is more preferable because of the stability of the compound and ease of synthesis.

Similarly, at least one of Xe ¹ , Xe ² , Ye ¹ , Ye ² , Ze ¹ and Ze ² in the general formula (E) is preferably a 1,2-phenylene group or a 1,3- More preferably one of Xe ¹ and Xe ² , at least one of Ye ¹ and Ye ² , or at least two of Ze ¹ and Ze ^2, is 1,2-phenyl Phenylene group, and most preferably a 1,3-phenylene group.

As the aromatic heterocyclic ring forming an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent, monocyclic rings of 5 or 6-membered rings, or 2 to 5 condensed rings thereof are preferable. Specific examples include furan ring, benzofuran ring, dibenzofuran ring, thiophene ring, benzothiophene ring, dibenzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, A thiophenol ring, a thiophenol ring, a furfuran ring, a thienofuran ring, a benzoisooxazole ring, a benzoisooxazole ring, a benzoisooxazole ring, a benzoisooxazole ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a perimidine ring, a quinazoline ring , And quinazolinone rings. Among them, from the viewpoint of the stability of the compound and the high charge transporting property, it is preferably a carbazole ring, a dibenzofuran ring or a dibenzothiophene ring, and from the viewpoint of high electron transporting property, a pyridine ring, a pyrimidine ring, Triazine ring.

Xa ³ , Ya ³ and Za ³ in the general formula (A) and Xe ³ , Ye ³ and Ze ³ in the general formula (E) are each independently a hydrogen atom, a carbon number which may have a substituent An aromatic hydrocarbon group of 6 to 30 carbon atoms or an aromatic heterocyclic group of 3 to 30 carbon atoms which may have a substituent.

As the aromatic hydrocarbon ring which forms an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocycle of 6-membered rings or a condensed ring of 2 to 5 is preferable. Specifically, examples of Xa ¹ in the general formula (A) include the same rings as described above. Among them, benzene ring, naphthalene ring or phenanthrene ring is preferable in view of the stability of the compound.

As the aromatic heterocyclic ring forming an aromatic heterocyclic group having 3 to 30 carbon atoms which may have a substituent, monocyclic rings of 5 or 6-membered rings, or 2 to 5 condensed rings thereof are preferable. Specifically, examples of Xa ¹ and the like in the general formula (A) include the same rings as described above. Among them, carbazole ring, dibenzofuran ring or dibenzothiophene ring is preferable in view of the stability of the compound and the charge transporting property.

The general formula (A) the three substituents of Hetero structure ^{in, -Xa 1 -Xa 2 -Xa 3,} -Ya 1 -Ya 2 -Ya 3, and, -Za ¹ -Za ² -Za ³ are the same The chart may be different. It is preferable that at least one is different in terms of lowering the symmetry of the compound and increasing solubility in a solvent.

-Xe ¹ -Xe ² -Xe ³ , -Ye ¹ -Ye ² -Ye ³ , and -Ze ¹ -Ze ² -Ze ^{3, which} are three substituents of N in the general formula (E) . It is preferable that at least one is different in terms of lowering the symmetry of the compound and increasing solubility in a solvent.

Examples of the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group may have include a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, an aromatic heterocyclic group having 3 to 20 carbon atoms, a diaryl group having 12 to 60 carbon atoms An amino group, an alkyloxy group having 1 to 20 carbon atoms, a (hetero) aryloxy group having 3 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a (hetero) arylthio group having 3 to 20 carbon atoms, have. Among them, a saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 25 carbon atoms are preferable in view of solubility and heat resistance. In addition, from the viewpoint of the stability of the compound, it is also preferable to have no substituent.

Specific examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Hexyl group, decyl group and octadecyl group. Among these, methyl group, ethyl group and isopropyl group are preferable, and methyl group and ethyl group are more preferable in view of easiness of obtaining raw material and low cost.

Examples of the monovalent aromatic hydrocarbon group having 6 to 25 carbon atoms include a naphthyl group such as phenyl group, 1-naphthyl group and 2-naphthyl group, a phenanthyl group such as 9-phenanthyl group and 3-phenanthyl group, A naphthacenyl group such as a 1-naphthacenyl group and a 2-naphthacenyl group, a 1-cresinyl group, a 2-cresenyl group, a 3-cresenyl group, A pyrenyl group such as a 1-pyrenyl group, a triphenylrenyl group such as a 1-triphenylrenyl group, a 1-chlorophenyl group such as a 1-chlorophenyl group, A biphenyl group of a 3-biphenyl group, a group having a fluoranthene ring, a group having a fluorene ring, a group having an acenaphthene ring, a substituent having a benzopyrene ring, etc. . Among them, phenyl group, 2-naphthyl group and 3-biphenyl group are preferable from the viewpoint of stability of the compound, and phenyl group is particularly preferable for ease of purification.

Examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include a thienyl group such as 2-thienyl group, a furyl group such as 2-furyl group, an imidazolyl group such as 2-imidazolyl group, A pyridyl group such as a 2-pyridyl group, and a triazinyl group such as a 1,3,5-triazin-2-yl group. Among them, a carbazolyl group, particularly a 9-carbazolyl group, is preferable from the standpoint of stability.

Examples of the diarylamino group having 12 to 60 carbon atoms include a diphenylamino group, an N-1-naphthyl-N-phenylamino group, an N-2-naphthyl-N-phenylamino group, , An N- (biphenyl-4-yl) -N-phenylamino group, and a bis (biphenyl-4-yl) amino group. Among them, a diphenylamino group, an N-1-naphthyl-N-phenylamino group and an N-2-naphthyl-N-phenylamino group are preferable, and a diphenylamino group is particularly preferable in view of stability.

Examples of the alkyloxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group, and an octadecyloxy group.

Examples of the (hetero) aryloxy group having 3 to 20 carbon atoms include substituents having a heteroaryloxy group such as an aryloxy group such as a phenoxy group, a 1-naphthyloxy group, a 9-anthraniloxy group and a 2-thienyloxy group, have.

Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an isopropylthio group and a cyclohexylthio group.

Examples of the (hetero) arylthio group having 3 to 20 carbon atoms include arylthio groups such as phenylthio group, 1-naphthylthio group and 9-anthranthylthio group, and heteroarylthio groups such as 2-thienylthio group and the like .

Although the light-emitting layer has been described above, the other structures will be described below.

[Board]

As for the substrate, the above-described substrate can be used. Of these, inorganic glass is preferable.

[anode]

The anode fulfills the role of hole injection into the layer (the hole injection layer, the light emitting layer, or the like) on the light emitting layer side. The anode is usually made of a metal such as aluminum, gold, silver, nickel, palladium, platinum or the like, a metal oxide such as indium and / or tin oxide, a halogenated metal such as copper iodide, carbon black, Thiophene), polypyrrole, polyaniline, and the like. The formation of the anode is usually performed by a sputtering method, a vacuum deposition method, or the like. In the case of metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, the anode may be formed by dispersing in a suitable binder resin solution and applying the dispersion onto a substrate . In the case of the conductive polymer, a thin film may be formed directly on the substrate by electrolytic polymerization, and a conductive polymer may be applied on the substrate to form a cathode (Applied Physics Letters, 1992, Vol. 60, pp. 2711 Reference). The positive electrode may be formed by laminating with different materials.

The thickness of the anode depends on the required transparency. When transparency is required, it is preferable that the transmittance of visible light is normally 60% or more, preferably 80% or more. In this case, the thickness is usually 5 nm or more, preferably 10 nm or more, To 1000 nm or less, preferably 500 nm or less. When it may be opaque, the anode may be the same as the substrate. Further, it is also possible to laminate different conductive materials on the positive electrode.

Further, it is preferable to treat the surface of the anode with ultraviolet (UV) / ozone treatment, oxygen plasma or argon plasma treatment for the purpose of removing impurities adhering to the anode and adjusting the ionization potential to improve the hole injection property.

[Hole injection layer]

The hole injection layer is a layer for injecting and transporting holes from the anode toward the light emitting layer.

As a material for forming the hole injection layer, it is preferable that it is a material which has high hole transporting ability and can efficiently transport the injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is high, the stability is excellent, and impurities which become traps do not occur at the time of production or use. In many cases, it is preferable that the light emitting layer is in contact with the light emitting layer, so that light emission from the light emitting layer is not extinguished, or exciplex is formed between the light emitting layer and the light emitting layer.

As the material of such a hole injection layer, besides the above-described polymer compound, a material conventionally used as a constituent material of the hole injection layer can be used. For example, there may be mentioned arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, An oligothiophene derivative, a condensed polycyclic aromatic derivative, and a metal complex.

In addition, examples thereof include polyvinylcarbazole derivatives, polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylenevinyl A phenylene derivative, a phenylene naphthalene derivative, a phenylene norbornene derivative, a phenylene norbornene derivative, a phenylene norbornene derivative, a phenylene norbornene derivative, and the like. These may be any of an alternating (co) polymer compound, a random polymer compound, a block polymer compound, or a graft homopolymer compound. In addition, it may be a polymer having three or more terminals at the main chain and a so-called dendrimer.

Of these, polyarylamine derivatives and polyarylene derivatives are preferred because of their high hole-transporting capability.

The polyarylamine derivative preferably contains a repeating unit represented by the following formula (2).

(40)

Ar ²¹ and Ar ²² each independently represent an aromatic hydrocarbon group which may have a direct bond or a substituent or an aromatic heterocyclic group which may have a substituent and Ar ²³ to Ar ²³ each independently represent an aromatic heterocyclic group which may have a substituent, And Ar ²⁵ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, T ² is selected from the above-mentioned crosslinkable groups T and T ' Is preferred.

(41)

(The benzocyclobutene ring in the formula (3) may have a substituent, and the substituents may be bonded to each other to form a ring.)

It is further preferable that the hole injection layer is the conductive thin film of the present invention.

&Lt; Composition for forming hole injection layer &gt;

When the hole injecting layer is formed by a wet film forming method, the hole transporting compound constituting the hole injecting layer and, if necessary, other components are mixed with an appropriate solvent to form a film forming composition (for forming the hole transporting layer of the hole injecting layer Composition) is prepared and used.

The content of the hole-transporting compound in the composition for forming a hole injection layer is usually 0.1% by weight or more, preferably 0.5% by weight or more, usually 50% by weight or less, and preferably 20% by weight or less. The composition for forming a hole injection layer may contain two or more kinds of hole-transporting compounds, and in that case, it is preferable that the total of two or more kinds is within the above range

The composition for forming a hole injection layer according to the present invention usually comprises a solvent.

The solvent contained in the composition for forming a hole injection layer according to the present invention is not particularly limited, but usually 0.1 wt%, preferably 0.5 wt%, more preferably 1.0 wt% or more of the hole-transporting compound is dissolved Lt; / RTI &gt;

Specific examples of the boiling range of the solvent are the same as those of the solvent usable in the composition containing the conductive thin film forming material of the present invention described above.

<Electron-Soluble Compound>

The hole injecting layer preferably contains an electron-accepting compound because it can improve the conductivity of the hole injecting layer by oxidation of the hole transporting compound.

The electron-accepting compound is preferably a compound having an oxidizing power and capable of accepting one electron from the above-described hole-transporting compound. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound having an electron affinity of 5 eV or more Compound is more preferable.

Examples of such an electron-accepting compound include a triarylboron compound, a halogenated metal, a Lewis acid, an organic acid, an onium salt, a salt of an arylamine and a metal halide, a salt of an arylamine and a Lewis acid Species or compounds of two or more kinds. Specific examples thereof include onium salts substituted with organic groups such as triphenylsulfonium tetrafluoroborate, iron chloride (III) (Japanese Patent Laid-Open No. 11-251067), inorganic compounds of high-valency such as ammonium peroxodisulfate; Aromatic compounds such as tris (pentafluorophenyl) borane (Japanese Unexamined Patent Application Publication No. 2003-31365); ionic compounds disclosed in International Publication WO 2005/089024; fullerene derivatives And iodine.

Of the above compounds, an onium salt substituted with an organic group and an inorganic compound of a high-valent organic group are preferable in that they have a strong oxidizing power. From the viewpoint of high solubility in an organic solvent and easy formation of a film by a wet film forming method, an onium salt substituted with an organic group, a cyano compound, and an aromatic boron compound are preferable.

Specific examples of the organic compound-substituted onium salt, cyano compound or aromatic boron compound suitable as the electron-accepting compound include those described in WO 2005/089024, and preferred examples thereof are also the same.

Specific examples of the electron-accepting compound in the present invention are shown below, but the present invention is not limited thereto. In addition, the following general formula (I-1) n1 of the following general formula (I-2) n2 in the following formula (I-3) of n3 is counter anion Z ~ Z ^{n1- n3-} ionic valency of each independently Quot; is a positive integer. The value of n1 to n3 is not particularly limited, but is preferably 1 or 2, and most preferably 1.

1 to 48, 54, 55, 60 to 62, 64 to 75, 79 to 83, B-1 to 20, 24, 25, and 25 from the viewpoints of the electron accepting property, the heat resistance, 1 to 9, 12 to 15, 17, 19, 24, and 29 are preferable, and compounds represented by the following formulas , 31 to 33, 36, 37, 65, 66, 69, 80 to 82, B-1 to 3, 5, 7 to 10, 16, 30, 33, 39, S-1 to 3, , 25, 31 are more preferable, and compounds of A-1 to 7, 80 are particularly preferable.

The electron-accepting compound may be used singly or two or more kinds may be used in any combination and ratio.

The content of the electron-accepting compound in the composition for forming a hole injection layer is usually 0.01% by weight or more, preferably 0.05% by weight or more, usually 20% by weight or less, and preferably 10% by weight or less. The composition for forming a hole injection layer may contain two or more kinds of electron-accepting compounds, and in that case, it is preferable that the total of two or more kinds is within the above range.

<Cationic Radical Compound>

The hole injection layer preferably contains a cation radical compound in terms of enhancing the hole injection property from the anode and enhancing hole transportability.

As the cationic radical compound, a cationic radical, which is a chemical species in which one electron is removed from the hole-transporting compound, and an ionic compound comprising a counteranion are preferable. However, when the cation radical is derived from a polymer compound having a hole-transporting property, the cation radical is a structure in which one electron is removed from the repeating unit of the polymer compound.

As the cationic radical, a compound which is one electron-eliminated from the above-described compound as the hole-transporting compound is preferable from the viewpoints of non-crystallinity, transmittance of visible light, heat resistance, and solubility.

Here, the cationic radical compound can be produced by mixing the above-described hole-transporting compound with an electron-accepting compound. That is, by mixing the above-described hole-transporting compound with the electron-accepting compound, electron transfer from the hole-transporting compound to the electron-accepting compound occurs, and a cationic radical compound comprising the cationic radical of the hole-transporting compound and the counteranion is produced.

Cationic radical compounds derived from macromolecules such as PEDOT / PSS (Adv. Mater., 2000, vol. 12, p. 481) or emeraldine hydrochloride (J. Phys. Chem., 1990, volume 94, page 7716) But also by oxidation polymerization (dehydrogenation polymerization).

The oxidation polymerization referred to herein is a chemical or electrochemical oxidation of monomers in an acidic solution using peroxo-2-sulfate or the like. In the case of the oxidation polymerization (dehydrogenation polymerization), the monomer is oxidized to polymerize, and a cationically eliminated cationic radical is generated from the repeating unit of the polymer, in which the anion derived from the acidic solution is a counteranion.

<Film Forming Method>

When the hole injecting layer is formed by the wet film forming method, it can be applied and dried in the same manner as the application method of the conductive thin film forming composition of the present invention. Drying may be carried out more than once.

When the hole injecting layer is the conductive thin film related to the present invention, it has the above-described infrared heating process.

&Lt; Film Thickness of Hole Injection Layer &gt;

The film thickness of the hole injection layer is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

[Hole transport layer]

The hole transporting layer in the present invention is a layer formed on the hole injecting layer and transporting holes transported from the hole injecting layer to the light emitting layer.

As the material for forming the hole transporting layer, it is preferable that it is a material which has a high hole transporting property and is capable of efficiently transporting the injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is high, the stability is excellent, and impurities which become traps do not occur at the time of production or use. Further, in many cases, it is preferable not to quench the light emission from the light emitting layer or to form an exciplex with the light emitting layer to decrease the efficiency because it contacts the light emitting layer.

Such a material for forming the hole transporting layer may be a compound including the structure and the like described in the section of the above-mentioned [hole injection layer]. However, from the viewpoint of excellent charge transport ability and solubility in organic solvents, Is preferably a polymer compound containing a repeating unit represented by the following formula

(42)

(In the formula (5), q represents an integer of 0 to 3, Ar ¹¹ and Ar ¹² each independently represent an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent or a direct bond, Ar ¹³ to Ar ¹⁵ each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.

Provided that both of Ar ¹¹ and Ar ¹² are not a direct bond.

In the formula (5), Ar ¹¹ and Ar ¹² each independently represent a direct bond, an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and Ar ¹³ to Ar ¹⁵ each independently represent a substituent An aromatic hydrocarbon group which may be present or an aromatic heterocyclic group which may have a substituent.

Examples of the aromatic hydrocarbon group which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, , An acenaphthene ring, a fluoranthene ring, a fluorene ring and the like, or a group derived from two to five condensed rings of a six-membered ring.

Examples of the aromatic heterocyclic group which may have a substituent include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, A thiophenol ring, a thiophenol ring, a thiophenol ring, a thienophenol ring, a benzoisooxazole ring, a benzoisooxazole ring, a benzoisooxazole ring, a benzothiophene ring, A pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring , Quinoline or 2 to 4 condensed ring-derived groups of 5 or 6-membered rings such as quinazoline ring, quinazolinone ring and azulene ring.

Ar ¹¹ to Ar ¹⁵ each independently represent a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, a fluorene ring A group derived from a ring is preferable.

As Ar ¹¹ to Ar ¹⁵ , bivalent groups in which one or more rings selected from the above-mentioned groups are directly bonded or linked by -CH═CH- group are preferable, and biphenylene group and terphenylene group are more preferable desirable.

The substituent group that the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar ¹¹ to Ar ¹⁵ may have in addition to the insolubilizing group described later is not particularly limited and includes, for example, one or two selected from Substituent Group Z More than species.

<Substituent group Z>

An alkyl group of 1 to 24 carbon atoms, more preferably a carbon number of 1 to 12, such as a methyl group and an ethyl group, an alkenyl group of 2 to 24 carbon atoms, more preferably a carbon number of 2 to 12, such as a vinyl group, Preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms; alkoxy groups such as methoxy groups and ethoxy groups, preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as phenoxy An aryloxy group having preferably 4 to 36 carbon atoms and more preferably 5 to 24 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group such as a methoxycarbonyl group, a naphthoxy group and a pyridylox group, preferably having 2 to 24 carbon atoms, An alkoxycarbonyl group preferably having 2 to 12 carbon atoms;

A dialkylamino group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms such as a dimethylamino group and a diethylamino group, a diphenylamino group, a ditolylamino group and an N-carbazolyl group, A diarylamino group having a carbon number of 12 to 36, more preferably a carbon number of 12 to 24, an arylalkylamino group having preferably 6 to 36 carbon atoms and more preferably 7 to 24 carbon atoms such as a phenylmethylamino group, an acetyl group and a benzoyl group Preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, a halogen atom such as a fluorine atom or a chlorine atom, a trifluoromethyl group or the like preferably having 1 to 12 carbon atoms, A haloalkyl group of 6;

An alkylthio group having 1 to 24 carbon atoms and more preferably 1 to 12 carbon atoms such as a methylthio group and an ethylthio group; an alkylthio group such as a phenylthio group, a naphthylthio group and a pyridylthio group preferably having 4 to 36 carbon atoms , An arylthio group having 5 to 24 carbon atoms, more preferably a silyl group having 2 to 36 carbon atoms, and more preferably 3 to 24 carbon atoms, such as trimethylsilyl group and triphenylsilyl group; a trimethylsiloxy group, A siloxy group having preferably 2 to 36 carbon atoms, more preferably 3 to 24 carbon atoms such as a siloxy group, a cyano group, a phenyl group and a naphthyl group preferably having 6 to 36 carbon atoms, more preferably 6 to 24 carbon atoms Aromatic heterocyclic groups preferably having 3 to 36 carbon atoms, more preferably 4 to 24 carbon atoms, such as an aromatic hydrocarbon group, a thienyl group and a pyridyl group.

Each of the above substituents may further have a substituent, and examples thereof include the groups exemplified in the above substituent group Z. [

The molecular weight of the substituent group that Ar ² to Ar ¹⁵ may have in addition to the insolubilized group to be described later is preferably 500 or less, more preferably 250 or less, including further substituted groups.

From the viewpoint of solubility, the substituents which the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar ¹¹ to Ar ¹⁵ may have are independently an alkyl group of 1 to 12 carbon atoms and an alkoxy group of 1 to 12 carbon atoms.

<Description of q>

In the above formula (5), q represents an integer of 0 to 3.

q is usually at least 0, usually at most 3, preferably at most 2. When q is 2 or less, it is easy to synthesize monomers as raw materials.

&Lt; Percentage of repeating units &

The polymer compound for forming the hole transporting layer in the present invention is preferably a polymer compound containing one or more repeating units represented by formula (5).

In the case where the polymer compound for forming the hole transporting layer in the present invention has two or more repeating units, random copolymers, alternating copolymers, block copolymers and graft copolymers can be mentioned. From the standpoint of solubility in solvents, it is preferable to be a random copolymer. It is preferable to be an alternating copolymer in that charge transfer ability can be further increased.

&Lt; Cross-linking agent &

The polymer compound for forming the hole transporting layer in the present invention preferably has a crosslinkable group selected from the above-mentioned crosslinkable groups T and T '. The crosslinkable group is preferably a benzocyclobutene ring represented by the formula (3).

<Dissection>

The polymer compound for forming the hole transporting layer in the present invention may have a dissociation unit. Here, the term &quot; dissociation group &quot; refers to a group that dissociates from the bound aromatic hydrocarbon ring at 70 DEG C or higher and is also soluble in a solvent. Here, indicating solubility to a solvent means that the compound dissolves in toluene at room temperature at 0.1 wt% or more in the state before the reaction by irradiation with heat and / or active energy rays, and the solubility of the compound in toluene is preferably Is at least 0.5% by weight, more preferably at least 1% by weight. Such a dissociation group is preferable because it has excellent charge transport ability after the dissociation reaction.

Such a dissociation group is preferably a group dissociating thermally without forming a polar group on the side of the aromatic hydrocarbon ring, and more preferably a group dissociated thermally by a reverse dilution Alder reaction.

Furthermore, it is preferable that the group is a group which dissociates thermally at 100 캜 or higher, and a group which dissociates thermally at 300 캜 or lower.

Specific examples of the dissociation group are as follows, but the present invention is not limited thereto.

Specific examples of the case where the dissociation group is a divalent group are the same as those of the following <dissociation group 2>.

<The Harry Group A of the Two Guys>

(43)

A specific example of the case where the dissociation group is a monovalent group is the same as the following <dissociation group B> of the following formula 1.

<Harry Giggles B of 1 Street>

(44)

Specific examples of the polymer compound used in the above-described hole injection layer and hole transport layer include those described in JP-A-2009-263665 and JP-A-2010-239127.

Further, it is more preferable that the hole transporting layer is the conductive thin film of the present invention.

&Lt; Composition for forming a hole transporting layer &gt;

The hole transporting layer is formed by a wet film forming method. The wet film-forming method is not limited so long as it does not significantly impair the effect of the present invention. However, the solvent, the additive, the drying method, and the coating method in the composition for forming the hole transport layer are not limited to the items And the like.

<Film Thickness of Hole Transport Layer>

The film thickness of the hole transporting layer is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

[Hole blocking layer]

A hole blocking layer may be formed between the light emitting layer and an electron injection layer described later. The hole blocking layer is a layer laminated on the light emitting layer so as to be in contact with the interface on the cathode side of the light emitting layer.

The hole blocking layer serves to prevent holes from the anode from reaching the cathode and to efficiently transport electrons injected from the cathode in the direction of the light emitting layer.

Properties required for the material constituting the hole blocking layer include those having a high electron mobility and a low hole mobility, a material having a large energy gap (difference between HOMO and LUMO), a material having a high excitation triplet level (T1) . Examples of the material of the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8- quinolinolato) (2-methyl-8-quinolato) aluminum-ux-oxo-bis- (2-methyl-8-quinolylato) aluminum 2 nuclear metal complex (4-biphenyl) -4-phenyl-5- (4-tert-butylphenyl) -1,3,4-thiadiazole 1,2,4-triazole (JP-A-7-41759), and phenanthroline derivatives such as bazocuproline (JP-A-10-79297) . Also, a compound having at least one pyridine ring substituted at the 2, 4 and 6 positions described in WO 2005-022962 is also preferable as a material for the hole blocking layer.

There is no limitation on the method of forming the hole blocking layer. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

The film thickness of the hole blocking layer is arbitrary as long as it does not significantly impair the effect of the present invention, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

[Electron transport layer]

The electron transporting layer is formed between the light emitting layer and the electron injection layer for the purpose of further improving the current efficiency of the device.

The electron transporting layer is formed of a compound capable of efficiently transporting electrons injected from the cathode in the direction of the light emitting layer between electrodes to which an electric field is applied. The electron transporting compound used in the electron transporting layer is required to be a compound capable of efficiently injecting electrons with high electron injection efficiency from the cathode or electron injection layer and high electron mobility.

Examples of the material satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP-A 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole Or a derivative thereof, a thiazolidine derivative, a thiazolidine derivative, a thiazolidine derivative, a distyrylbiphenyl derivative, a silole derivative, a 3- or 5-hydroxyflavone metal complex, a benzoxazole metal complex, a benzothiazole metal complex, trisbenzimidazolylbenzene (US Patent No. 5,645,948) (JP-A No. 6-207169), a phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinone diimine , n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenide.

The film thickness of the electron transporting layer is usually about 1 nm, preferably about 5 nm, and the upper limit is usually about 300 nm, preferably about 100 nm.

The electron transporting layer is formed by laminating on the hole blocking layer by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. Vacuum deposition is usually used.

[Electron injection layer]

The electron injection layer efficiently injects electrons injected from the cathode into the electron transporting layer or the light emitting layer.

For efficient electron injection, a material having a low work function is preferable as a material for forming the electron injection layer. Examples thereof include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is preferably 0.1 nm or more and 5 nm or less.

Further, an alkali metal such as sodium, potassium, cesium, lithium, or rubidium may be added to an organic electron transporting material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as a bazophenanthroline described below or an aluminum complex of 8- (Japanese Unexamined Patent Application, First Publication No. Hei 10-270171, Japanese Unexamined Patent Application, First Publication No. 2002-100478, and Japanese Unexamined Patent Application, First Publication No. 2002-100482), it is possible to improve the electron injecting and transporting property, . In this case, the film thickness is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

The electron injection layer is formed by laminating a light-emitting layer or a hole blocking layer thereon by a wet film formation method or a vacuum deposition method.

The details of the wet film formation method are the same as those of the hole injection layer and the light emitting layer.

On the other hand, in the case of the vacuum vapor deposition method, an evaporation source is placed in a crucible or a metal boat provided in a vacuum container, the inside of the vacuum container is evacuated to about 10 ^-4 Pa by a suitable vacuum pump, An electron injection layer is formed on a luminescent layer, a hole blocking layer or an electron transporting layer on a substrate facing a crucible or a metal boat.

The deposition of the alkali metal as the electron injecting layer is carried out by using an alkali metal chromium oxide and an alkali metal dispenser filled with a reducing agent in nichrome. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced to evaporate the alkali metal. When the organic electron transporting material and the alkali metal are co-deposited, the organic electron transporting material is placed in a crucible provided in a vacuum container, and the inside of the vacuum container is evacuated to about 10 ^-4 Pa with a suitable vacuum pump. Is evaporated at the same time, and an electron injecting layer is formed on the substrate facing the crucible and the dispenser.

At this time, co-deposition is uniformly performed in the film thickness direction of the electron injection layer, but there may be a concentration distribution in the film thickness direction.

[cathode]

The cathode fulfills the role of injecting electrons into the layer (the electron injection layer or the light emitting layer) on the light emitting layer side. As a material for the negative electrode, a material used for the positive electrode can be used. In order to efficiently inject electrons, a metal having a low work function is preferable, and a suitable material such as tin, magnesium, indium, calcium, Metals or their alloys are used. As specific examples, a low-function alloy electrode such as a magnesium-silver alloy, a magnesium-indium alloy, and an aluminum-lithium alloy may be used.

The film thickness of the cathode is usually the same as that of the anode.

It is preferable to laminate a metal layer having a high work function and stable with respect to the atmosphere thereon for the purpose of protecting the negative electrode made of a low-function metal, because stability of the device is increased. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used.

[Etc]

The organic electroluminescent device in the present invention may have another configuration within a range that does not deviate from the purpose. For example, an optional layer may be provided between the anode and the cathode in addition to the above-described layer, and any layer may be omitted between the anode and the cathode as long as the performance is not impaired.

The cathode, the electron injection layer, the light emitting layer, the hole injection layer, and the anode may be laminated in this order on the substrate, that is, on the substrate. In this case, The organic electroluminescent device of the present invention can be formed.

Further, it is also possible to adopt a structure in which a plurality of layer structures are stacked (a structure in which a plurality of light emitting units are stacked). At this time, if, for example, V ₂ O ₅ or the like is used as the charge generation layer (CGL) instead of the interfacial layer (between the light emitting units) (the anode is ITO and the cathode is Al) It is more preferable in terms of current efficiency and driving voltage.

The present invention can be applied to any device in which the organic electroluminescent devices are arranged as a single device or an array, or a structure in which the anode and the cathode are arranged in an X-Y matrix.

7. Organic EL display and organic EL lighting

The organic EL display and the organic EL illumination in the present invention use the organic electroluminescent element according to the present invention as described above. The type and structure of the organic EL display and the organic EL illumination in the present invention are not particularly limited, and the organic electroluminescence device of the present invention can be used to assemble according to a conventional method.

For example, the organic EL display according to the present invention can be manufactured by the method described in &quot; Organic EL Display &quot; (Oompa, published on August 20, 2004, Shizuoka Tokido, Tadashi Adachi, Hideyuki Murata) And organic EL illumination can be formed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily changed without departing from the gist of the present invention.

Example

(Example 1)

An inorganic glass substrate (alkali-free glass) having a thickness of 0.7 mm was used as a substrate. The inorganic glass substrate had a minimum value of the infrared ray transmittance at a wavelength of 2.8 mu m and its infrared ray transmittance was 39.6%.

On this inorganic glass substrate, a transparent conductive film of indium-tin oxide (ITO) was deposited to a thickness of 70 nm (manufactured by SANYO KOGYO CORPORATION, sputtered film formation) was subjected to a general photolithography technique and hydrochloric acid etching to produce 2 Mm-width stripe to form a positive electrode. The patterned ITO substrate was washed with ultrasonic cleaning with an aqueous solution of a surfactant, washing with ultrapure water, ultrasonic cleaning with ultrapure water and washing with ultrapure water in this order, followed by drying with compressed air, followed by ultraviolet ozone cleaning .

<Hole injection layer>

100 parts by weight of a high molecular compound (weight average molecular weight (Mw) = 98000, dispersion degree (Mw / Mn) = 1.66) represented by the following formula (P1), 4-isopropyl- (2.5% by weight) was prepared using 20 parts by weight of diphenyliodonium tetrakis (pentafluorophenyl) borate as a solvent and ethyl benzoate as a solvent, and then a PTFE (poly Filtration using a membrane filter made of tetrafluoroethylene) to prepare a coating composition.

[Chemical Formula 45]

This coating composition was spin-coated on the substrate. The number of revolutions of the spin coat was 4000 rpm, and the time was 30 seconds. After spin-coating, the solvent was dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the periphery of the glass substrate was wiped with toluene. The film thickness at this time was approximately 35 nm.

<Plasticity>

The substrate was heated to 30 占 폚 to 230 占 폚 by using a halogen heater (manufactured by Ushio Inc., heater peak wavelength: 1.2 占 퐉) as electromagnetic wave heating.

At this time, the product? Of the wavelength in the minimum value of the absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the halogen heater was 3.4 占 퐉 ² .

The temperature of the substrate was measured by using an infrared camera (manufactured by NEC Avio Infrared Technologies) and measuring the exposed portion of the glass substrate (the periphery of the glass substrate wiped with toluene).

The heating time was 3 minutes. The rate of temperature rise was 140 ° C / min for the initial 30 seconds. The time for reaching 150 캜 was one minute after the start. That is, the firing temperature condition was 2 minutes at a temperature of 150 占 폚 or more. During this time, the temperature was always rising, and was not maintained at a constant temperature. Further, a value (? / T) obtained by dividing? By a time t when the substrate was maintained at a temperature of 150 占 폚 or more was 0.028 占 퐉 ² / s.

The above process was carried out under the atmosphere. Thus, a hole injection layer was obtained.

&Lt; Hole transport layer &

A hole transport layer coating liquid of 1.0 wt% was prepared using cyclohexylbenzene as a solvent by using a polymer material (weight average molecular weight (Mw) = 57000, dispersion degree (Mw / Mn) = 1.9) shown in the following formula The hole transport layer coating liquid was spin-coated on the previously prepared hole injection layer under nitrogen, and the film was formed for 120 seconds at 2100 rpm of the spin coat. Thereafter, the solvent for 30 seconds was dried with a hot plate at 230 캜 The substrate was wiped with toluene around the periphery of the substrate. The baking was carried out by using a halogen heater in the same manner as in the case of baking the above-mentioned hole injection layer under air, Thus, a hole transporting layer was obtained.

(46)

<Light Emitting Layer>

25 parts by weight, 75 parts by weight, and 15 parts by weight of the compounds H1, H2 and D1 represented by the following formulas were respectively fed with 5.75 wt% of cyclohexylbenzene as a solvent to prepare a light emitting layer coating liquid. This luminescent layer coating liquid was spin-coated on the previously prepared hole transporting layer under nitrogen. The film was formed for 120 seconds at 1800 rpm of the spin coat. Thereafter, the periphery of the substrate was wiped off with toluene. After the film formation, the film was heated at 120 DEG C for 20 minutes by a hot plate. The film thickness at this time was 60 nm. Thus, a light emitting layer was obtained.

(47)

<Hole blocking layer>

Here, the light emitting layer was transferred into a vacuum evaporation apparatus, exhausted until the degree of vacuum in the apparatus became 1.8 x 10 &lt; ^-4 &gt; Pa or less, and then the compound (HB1) represented by the following formula was laminated to a film thickness of 10 nm by vacuum evaporation .

(48)

<Electron transport layer>

Subsequently, tris (8-quinolinolato) aluminum (Alq ₃ ) was deposited as an electron transporting material to a thickness of 30 nm by a vacuum deposition method.

<Electron injection layer>

Next, a stripe-shaped shadow mask having a width of 2 mm was adhered to the device so as to be orthogonal to the ITO stripe of the positive electrode, and lithium fluoride (LiF) was deposited to a film thickness of 0.5 nm .

<Cathode>

Subsequently, an aluminum layer was laminated to a thickness of 80 nm as a cathode by a vacuum evaporation method using the above-described shadow mask.

<Sealing Treatment>

Next, in order to prevent the element from deteriorating due to moisture or the like in the air during storage, the sealing treatment was performed by the method described below.

In a nitrogen glove box, a photocurable resin 30Y-437 (manufactured by Three Bond Co., Ltd.) was applied to the outer periphery of a glass plate having a size of 23 mm x 23 mm with a width of about 1 mm and a water getter sheet Respectively. On this substrate, the substrate on which the negative electrode was formed was bonded so that the deposited surface was opposed to the desiccant sheet. Thereafter, ultraviolet light was irradiated only to the region where the photocurable resin was applied, and the resin was cured.

Thus, an organic electroluminescent device 1 having a light emitting area portion of 2 mm x 2 mm size was obtained.

(Example 2)

An organic electroluminescent device 2 was obtained in the same manner as in Example 1 except that the hole injecting layer and the hole transporting layer were fired for 6 minutes. In this firing, the temperature raising rate was 140 占 폚 / min from the start of heating to 30 seconds, and the time for reaching 150 占 폚 was one minute after the start. Thereafter, the temperature was further raised to 267 占 폚 in 3 minutes. That is, depending on the firing temperature condition, the time at 150 占 폚 or more was 5 minutes. Also,? / T was 0.011 占 퐉 ² / s.

(Comparative Example 1)

An organic electroluminescent device A was obtained in the same manner as in Example 1 except that the hole injection layer and the hole transport layer were fired in a hot air heating furnace (furnace temperature: 230 캜). The peak wavelength of infrared rays in the hot air heating furnace (230 DEG C) was found to be 5.76 mu m by the following bin equation.

Bin equation: peak wavelength = 2897 / T (* T is the absolute temperature)

At this time, the product of the minimum transmittance of infrared rays in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of infrared rays was 16.1 탆 ² . In addition, the temperature of the substrate reached only 123 캜.

(Comparative Example 2)

An organic electroluminescent device B was obtained in the same manner as in Example 1 except that the hole injection layer and the hole transport layer were fired for 40 minutes. In this firing, the temperature raising rate was 140 占 폚 / min from the start of heating to 30 seconds, and the time for reaching 150 占 폚 was one minute after the start. Thereafter, the temperature was further raised to 280 DEG C for 12 minutes. The temperature was maintained at that temperature for an additional 27 minutes. According to the sintering temperature condition, the time of 150 DEG C or more was 39 minutes. Also,? / T was 0.0014 占 퐉 ² / s.

(Comparative Example 3)

An organic electroluminescent device C was obtained in the same manner as in Example 1 except that the firing time of the hole injecting layer and the hole transporting layer was 30 seconds. Also, in this firing, the temperature of the substrate reached only 100 캜.

(Example 3)

An organic electroluminescent device 3 was obtained in the same manner as in Example 1, except that an infrared heater (manufactured by Ushio Inc., heater peak wavelength: 2.5 mu m) having a ceramic coating method for firing the hole injecting layer and the hole transporting layer was used. Under the firing conditions using this heater, the time for reaching 150 占 폚 was 50 seconds after the start of heating. Thereafter, it was 230 deg. C for 2 minutes and 10 seconds. The product of the minimum value of the infrared ray transmittance in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of the ceramic heater coated with the infrared ray heater was 7.0 占 퐉 ² . Also,? / T was 0.026 占 퐉 ² / s.

(Example 4)

Except that PEDOT / PSS was used as the hole injecting layer. Thus, an organic electroluminescent device 4 was obtained. PEDOT / PSS (manufactured by Aldrich) was adjusted to 0.65 wt% by using water as a solvent and spin-coated. The film was formed at a spinning speed of 1000 rpm for 30 seconds.

(Comparative Example 4)

An organic electroluminescent device D was obtained in the same manner as in Example 4 except that the hole injection layer and the hole transport layer were sintered in a hot-air heating furnace (furnace temperature: 230 캜) instead of electromagnetic wave heating. In addition, the temperature of the substrate reached only 123 캜.

(Comparative Example 5)

An organic electroluminescent device E was obtained in the same manner as in Example 4 except that the hole injecting layer and the hole transporting layer were fired for 40 minutes. In this firing, the rate of temperature rise was 67 ° C / min from the start of heating to 3 minutes, and the time to reach 150 ° C was 50 seconds after the start. Thereafter, the temperature was further raised to 280 DEG C in 12 minutes. The temperature was maintained at that temperature for an additional 25 minutes. According to the sintering temperature condition, the time of 150 DEG C or more was 39 minutes and 10 seconds. Also,? / T was 0.0014 占 퐉 ² / s.

(Example 5)

An organic electroluminescent device 5 was obtained in the same manner as in Example 3 except that the firing process of the hole injection layer was performed with a far-infrared ceramic heater (manufactured by Nihon Kaya Co., Ltd., heater peak wavelength: 5.2 탆) for 3 minutes. The substrate temperature reached 150 DEG C after 120 seconds from the start. By the firing temperature condition, the time t of 150 ° C or more was 60 seconds. The product? Of a minimum value of infrared ray transmission in the wavelength range of 2000 to 3300 nm of the substrate and the peak wavelength of the far infrared ray ceramic heater was 14.6 占 퐉 ² . α / t was 0.24 μm ² / s.

(Example 6)

Except that the baking time of the hole injecting layer was changed to 6 minutes and the baking time of the hole transporting layer was further changed to 6 minutes to obtain an organic electroluminescence layer laminate element 6.

At this time, the substrate temperature reached 150 DEG C after 50 seconds from the start of heating. Thereafter, it was 270 DEG C for 5 minutes and 10 seconds. Also,? / T was 0.023 占 퐉 ² / s.

(Example 7)

An organic electroluminescent device 7 was obtained in the same manner as in Example 5, except that the firing method of the hole transport layer was changed to a far-infrared ceramic heater (manufactured by Nihon Kaisha Ltd., heater peak wavelength 5.2 탆) for 20 minutes. The substrate temperature reached 150 DEG C after 120 seconds from the start. By the firing temperature condition, the time t of 150 ° C or more was 18 minutes. ? / t was 0.013 占 퐉 ² / s.

Table 12 shows the results of measurement of the driving voltage and the current efficiency at 2500 cd / m 2 in Examples 1 to 7 and Comparative Examples 1 to 5.

In Examples 1 to 7, the driving voltage is low and the current efficiency is high, so that the performance as an organic electroluminescent device is high.

However, in Comparative Example 1 and Comparative Example 4, the driving voltage is high and the current efficiency is low. In the comparative example 2 and the comparative example 5, the driving voltage is high. In Comparative Example 3, the current efficiency is low.

(Example 8)

And an inorganic glass substrate having a thickness of 0.7 mm was used as a substrate. The inorganic glass substrate had a minimum value of the infrared transmittance at a wavelength of 2.8 mu m and its infrared transmittance was 68.84%.

On this inorganic glass substrate, an indium tin oxide (ITO) transparent conductive film was deposited to a thickness of 70 nm. The ITO substrate was cleaned by ultrasonic cleaning with an aqueous solution of a surfactant, washing with ultrapure water, ultrasonic cleaning with ultrapure water and washing with ultrapure water in this order, followed by drying with compressed air, followed by ultraviolet ozone cleaning.

<Hole injection layer>

100 parts by weight of a polymer compound (weight average molecular weight (Mw) = 39000, dispersion degree (Mw / Mn) = 1.8) represented by the following formula (P1 '), 100 parts by weight of 4-isopropyl- 15 parts by weight of methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate as a solvent were used to prepare a composition for forming a hole injection layer (5.50% by weight and 2.75% by weight).

(49)

(50)

This coating composition was spin-coated on the substrate. In order to obtain a desired film thickness, the number of revolutions of the spin coat was changed from 3000 rpm to 700 rpm. The rotation time was 30 seconds.

<Plasticity>

A halogen heater (manufactured by Ushio Inc., heater peak wavelength: 1.2 占 퐉) was used as infrared heating for the substrate. At this time, the product? Of the wavelength in the minimum value of the absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the halogen heater was 3.4 占 퐉 ² .

The irradiation time of the infrared ray was set to 1 minute. It was 70 ° C or more in 10 seconds from infrared irradiation. The maximum reachable temperature of the substrate was 160 ° C. The rate of temperature rise at this time was 180 占 폚 / min for the initial 30 seconds. The time t at which the substrate was 70 ° C or more was 50 seconds. ? / t was 0.067 占 퐉 ² / sec.

The above process was carried out under the atmosphere. The obtained initial film thickness was 52 nm to 345 nm.

&Lt; Residual film ratio &

This initial film thickness was immersed in cyclohexylbenzene, and after 10 seconds, cyclohexylbenzene was removed with a spin coater at a rotation speed of 1500 rpm for 30 seconds. Thereafter, cyclohexylbenzene was dried in a hot-air dryer at 230 DEG C for 5 minutes.

Thereafter, the film thickness (film thickness after dissolution) was measured. The residual film ratio was obtained by the following formula (9).

(%) = Film thickness after dissolution / initial film thickness 占 100 (9)

The obtained results are shown in Fig. At an initial film thickness of 50 nm to 345 nm, the residual film ratio was almost insoluble at 100%.

(Comparative Example 6)

Film formation, firing and residual film ratio were measured in the same manner as in Example 8 except that only the composition for the hole injection layer of 2.75% by weight was used, and the spinning speed of the spin coating was changed to 1,500 rpm at 4500 rpm. The initial film thicknesses were 21.4 nm, 34.4 nm and 40.4 nm. The results obtained are shown in Fig. As a result, it was found that the residual film ratio was low and the hole transporting material layer was not insoluble.

(Example 9)

Except that the number of revolutions of the spin coater was 1400 rpm, the firing method was a hot air furnace (furnace temperature 230 캜), and the firing time was 3 minutes to 60 minutes. Firing, and residual film ratios were measured. The initial film thickness was 150 nm. The results are shown in Fig. It was insoluble at 100% of the residual film ratio by heating for 45 minutes.

(Example 10)

Film formation, firing and residual film ratio measurement were carried out in the same manner as in Example 8 except that the polymer compound was replaced by the following formula (P3) (weight average molecular weight (Mw) = 58000 and dispersion degree (Mw / Mn) = 1.6) . The obtained initial film thickness was 5 points in total of 71 nm to 505 nm. The results are shown in Fig. The residual film ratio was almost 100%, and the polymer compound layer could be insolubilized.

(51)

(Comparative Example 7)

Film formation, firing, and residual film ratio were measured in the same manner as in Example 10 except that the composition for a hole injection layer of 2.75% by weight was used and the number of revolutions of the spin coat was changed to 4500 rpm and 2000 rpm. The obtained initial film thicknesses were 20.1 nm and 39.4 nm. The obtained results are shown in Fig. As a result, it was found that the residual film ratio was low and the hole transporting layer was not insolubilized.

(Example 11)

And the baking time was set to 2.5 minutes, the concentration of the composition for the hole transporting layer was set to 5.50 wt%, and the number of revolutions of the spin coat (number of revolutions per minute) An experiment was carried out in the same manner as in Example 10 except that the flow rate was 1400 rpm. The obtained initial film thickness was 200 nm. The residual film ratio was 100%.

At this time, the product? Of the wavelength at the minimum value of the absorption value in the range of 2000 nm to 3300 nm of the substrate and the peak wavelength of the halogen heater was 7.0 占 퐉 ² . It was 70 ° C or more in 10 seconds from infrared irradiation. The maximum reachable temperature of the substrate was 230 ° C. The rate of temperature rise at this time was 192 ° C / min for the initial 30 seconds. ? / t was 0.050 占 퐉 ² / sec.

(Comparative Example 8)

An experiment was carried out in the same manner as in Example 11 except that the concentration of the composition for the hole transport layer was 2.75% and the number of revolutions of the spin coat was 4500 rpm. The initial film thickness was 21 nm.

As a result, the residual film ratio was 0%, and the hole transporting material layer was not dissolved.

As described above, in Examples 8 to 11 in which the film thickness of the hole transporting layer was 50 nm or more and the predetermined baking process by infrared rays was performed, the hole transporting layer was insoluble. On the other hand, in Comparative Examples 6 to 8 in which the film thickness was 50 nm or less or the predetermined baking process was not performed, the hole transporting material layer was not sufficiently insolubilized.

(Example 12)

An organic electroluminescent device 8 was obtained in the same manner as in Example 1, except that the firing conditions of the hole injecting layer, the hole transporting layer, and the light emitting layer were changed as follows.

· Hole injection layer, hole transport layer:

And fired in a hot air furnace at 230 DEG C for 1 hour.

Light emitting layer:

For the firing of the light emitting layer, the temperature was raised from 30 占 폚 to 95 占 폚 for 1.5 minutes using a halogen heater (manufactured by Ushio Inc., heater peak wavelength: 1.2 占 퐉).

For measuring the temperature of the substrate, an exposed portion of the glass substrate was measured using an infrared camera (manufactured by NEC Avio Infrared Technologies).

The rate of temperature rise was 50 ° C / min for the initial 30 seconds. The temperature reached 70 ℃ after 48 seconds. That is, the time of 70 ° C or more was 42 seconds. During this time, the temperature was always rising, and the temperature was not maintained at a constant temperature. The firing process was carried out in the atmosphere. The film thickness at this time was 60 nm. Thus, a light emitting layer laminate 1 was obtained.

The product of the peak wavelength of the infrared heater at this time and the wavelength at the minimum transmittance of the glass substrate at a wavelength of 2000 nm to 3300 nm was 3.4 占 퐉 ² . α / t was 0.080 μm ² / s.

(Example 13)

An organic electroluminescent element 9 was produced in the same manner as in Example 12 except that the firing conditions of the light emitting layer were fired from 30 ° C to 110 ° C for 5 minutes.

The rate of temperature rise in the firing of the light emitting layer was 90 deg. C / min for the initial 30 seconds. After heating, the temperature reached 70 DEG C in 27 seconds. That is, the time of 70 ° C or more was 4 minutes and 33 seconds. The temperature reached 110 DEG C after 3 minutes after heating, and then the temperature remained constant until the end of firing. ? / t was 0.012 占 퐉 ² / s.

(Example 14)

An organic electroluminescent device 10 was produced in the same manner as in Example 13 except that a halogen heater of a ceramic coating (manufactured by Usuio Co., Ltd., heater peak wavelength: 2.5 mu m) was used as the firing condition of the light emitting layer.

The rate of temperature rise in the firing of the light emitting layer was 80 DEG C / min for the initial 30 seconds. After heating, the temperature reached 70 캜 in 30 seconds. That is, a time t of 70 ° C or more was 1 minute. During this time, the temperature was always rising, and was not maintained at a constant temperature. The temperature of the substrate reached 110 ° C at 1 minute 30 seconds from the start of heating.

The product of the peak wavelength of the infrared heater at this time and the wavelength at the minimum transmittance of the glass substrate at a wavelength of 2000 nm to 3300 nm was 7.0 탆 ² . α / t was 0.12 μm ² / s.

(Example 15)

An organic electroluminescent device 11 was obtained in the same manner as in Example 14 except that the following points were changed.

&Lt; Firing of hole injection layer and hole transport layer &gt;

The hole injection layer and the hole transport layer were fired using a halogen heater (manufactured by Ushio Co., Ltd., heater peak wavelength: 2.5 mu m) of a ceramic coating. The firing conditions were each fired for 3 minutes from 30 ° C to 230 ° C. The time for the substrate to reach 150 캜 was 50 seconds after the start of heating. Thereafter, it was 230 deg. C for 2 minutes and 10 seconds. The product? Of a minimum value of infrared transmission in a wavelength range of 2000 to 3300 nm of the substrate and a peak wavelength of a ceramic coated infrared heater was 7.0 占 퐉 ² . Also,? / T was 0.026 占 퐉 ² / s.

&Lt; Firing of light emitting layer &

The light emitting layer was fired in the same manner as in Example 14. [

(Comparative Example 9)

<High-temperature firing>

An organic electroluminescent element F was obtained in the same manner as in Example 12 except that the firing conditions of the light emitting layer were fired from 30 占 폚 to 193 占 폚 in 1.5 minutes. The rate of temperature rise in the firing of the light emitting layer was 150 DEG C / min for the initial 30 seconds.

(Comparative Example 10)

<Long-term firing>

An organic electroluminescent element G was obtained in the same manner as in Example 12 except that the firing conditions of the light emitting layer were fired at 30 ° C to 125 ° C for 25 minutes. After 28 seconds from the start of baking, the temperature reached 70 占 폚, and after 2 minutes, it reached 125 占 폚. Thereafter, the temperature was kept constant. That is, the time t held at 70 ° C or higher was 24 minutes and 32 seconds. Here,? / T was 0.002 占 퐉 ² / s.

Table 13 shows the characteristics of the devices obtained in Examples and Comparative Examples. The current efficiency shows a value at 10 mA / cm 2.

Thus, the organic electroluminescence devices 8 to 11 obtained in Examples 12 to 15 exhibited higher current efficiency than the organic electroluminescence laminates F and G obtained in Comparative Examples 9 and 10.

(Example 16)

An organic electroluminescent device 12 was obtained in the same manner as in Example 14 except that the following materials were used as substrates and the conditions for forming the hole injecting layer, the hole transporting layer, and the light emitting layer were changed as follows.

And an inorganic glass substrate having a thickness of 0.7 mm was used as a substrate. The inorganic glass substrate had a minimum value of the infrared transmittance at a wavelength of 2.8 mu m and its infrared transmittance was 68.84%.

An indium tin oxide (ITO) transparent conductive film was deposited on the inorganic glass substrate to a thickness of 110 nm. The ITO substrate was cleaned by ultrasonic cleaning with an aqueous solution of a surfactant, washing with ultrapure water, ultrasonic cleaning with ultrapure water and washing with ultrapure water in this order, followed by drying with compressed air, followed by ultraviolet ozone cleaning.

<Hole injection layer>

A composition for forming a hole injection layer of 2.5% by weight was prepared using 100 parts by weight of the polymer compound represented by the following formula (P4), 20 parts by weight of the compound represented by the formula (A1) and ethyl benzoate as a solvent.

(52)

This coating composition was spin-coated on the substrate. The number of revolutions of the spin coat was 1500 rpm, and the time was 30 seconds. After spin-coating, the solvent was dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the periphery of the glass substrate was wiped with toluene.

For baking the hole injection layer, a ceramic coated infrared heater (manufactured by Ushio Inc., heater peak wavelength: 2.5 mu m) was used. At this time, the product? Of the wavelength at the minimum value of the absorption value in the range of 2000 nm to 3300 nm and the peak wavelength of the infrared heater was 7.0 占 퐉 ² . The irradiation time of infrared rays was 7 minutes. The time for reaching 70 캜 was 10 seconds after the initiation of the infrared ray irradiation, and the time for reaching 150 캜 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 ° C or more was 6 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.019 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 50 nm.

&Lt; Hole transport layer &

A 2.5 wt% hole transporting layer coating liquid was prepared by using cyclohexylbenzene as a solvent as a polymeric material represented by the following formula (P5). This positive hole transport layer coating liquid was spin-coated on the previously prepared positive hole injection layer under nitrogen. The film was formed at a spinning speed of 1500 rpm for 100 seconds. Thereafter, the solvent for 30 seconds was dried with a hot plate at 230 캜. Thereafter, the periphery of the substrate was wiped off with toluene.

The firing was performed using the same infrared heater as the hole injection layer. The irradiation time of the infrared ray was set to 6 minutes. The time for reaching 150 캜 was 50 seconds after the infrared irradiation. Therefore, the time of 150 DEG C or more was 5 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.023 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 37 nm.

(53)

<Light Emitting Layer>

25 parts by weight, 75 parts by weight, and 10 parts by weight of the compounds H3, H4 and D2 represented by the following formulas were each liquid at 4.0 wt% using cyclohexylbenzene as a solvent to prepare a light emitting layer coating liquid. This luminescent layer coating liquid was spin-coated on the previously prepared hole transporting layer under nitrogen. The film was formed for 120 seconds at a spinning speed of 2500 rpm. Thereafter, the periphery of the substrate was wiped off with toluene. The light emitting layer was heated under the atmosphere using the same infrared heater as the hole injection layer. The heating time was 60 seconds. The rate of temperature rise in the firing of the light emitting layer was 80 DEG C / min for the initial 30 seconds. It reached 70 캜 in 30 seconds after heating, and the time t of 70 캜 or more was 30 seconds. During this time, the temperature was always rising, and was not maintained at a constant temperature. The temperature of the substrate reached 100 DEG C in 60 seconds from the start of heating. The film thickness of the light emitting layer was 54 nm.

The product of the peak wavelength of the infrared heater at this time and the wavelength at the minimum transmittance of the glass substrate at a wavelength of 2000 nm to 3300 nm was 7.0 탆 ² . α / t was 0.23 μm ² / s.

(54)

(Example 17)

An organic electroluminescent element 13 was produced in the same manner as in Example 16 except that the firing conditions of the light emitting layer were set under the following conditions.

The infrared irradiation time to the light emitting layer was 7 minutes. The rate of temperature rise in the firing of the light emitting layer was 80 DEG C / min for the initial 30 seconds. After heating, the temperature reached 70 캜 in 30 seconds. Therefore, the time t of 70 ° C or more was 6 minutes and 30 seconds. The temperature of the substrate reached 120 占 폚 in 3 minutes from the start of heating, and then was heated at a constant temperature of 120 占 폚. α / t was 0.018 μm ² / s.

(Example 18)

An organic electroluminescent device 14 was obtained in the same manner as in Example 16, except that the conditions for forming the hole injection layer and the hole transport layer were changed as follows.

<Hole injection layer>

A composition for forming a hole injection layer of 3.5% by weight was prepared by using 100 parts by weight of the polymer compound represented by the following formula (P6), 15 parts by weight of the compound represented by the formula (A1) and ethyl benzoate as a solvent.

(55)

This coating composition was spin-coated on the substrate. The number of revolutions of the spin coat was 1500 rpm, and the time was 30 seconds. After spin-coating, the solvent was dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the periphery of the glass substrate was wiped with toluene.

The firing was carried out using the same infrared heater as in Example 16. The irradiation time of the infrared ray was set to 10 minutes. The time for reaching 70 占 폚 was 10 seconds after the infrared ray irradiation, and the time for reaching 150 占 폚 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 ° C or more was 9 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.013 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 50 nm.

&Lt; Hole transport layer &

A 2.5 wt% hole transporting layer coating liquid was prepared by using cyclohexylbenzene as the solvent of the polymer material represented by the above formula (P5). This positive hole transport layer coating liquid was spin-coated on the previously prepared positive hole injection layer under nitrogen. The film was formed at a spinning speed of 1500 rpm for 100 seconds. Thereafter, the solvent for 30 seconds was dried with a hot plate at 230 캜. Thereafter, the periphery of the substrate was wiped off with toluene.

The firing was carried out using the same infrared heater as in Example 16. The irradiation time of the infrared ray was set to 10 minutes. The time for reaching 150 캜 was 50 seconds after the infrared irradiation. Therefore, the time of 150 ° C or more was 9 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.013 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 37 nm.

(Example 19)

An organic electroluminescent device 15 was produced in the same manner as in Example 16, except that the composition for forming the light emitting layer was set as follows.

<Light Emitting Layer>

25 parts by weight, 75 parts by weight and 10 parts by weight of the compounds H5, H6 and D3 represented by the following formulas, respectively, were used in place of cyclohexylbenzene as a solvent.

(56)

(Example 20)

The hole injecting layer and the hole transporting layer were formed in the same manner as in Example 18, and the light emitting layer was formed in the same manner as in Example 19 to prepare the organic electroluminescent device 16.

(Example 21)

An organic electroluminescent device 17 was produced in the same manner as in Example 20 except that the firing conditions of the light emitting layer were set under the following conditions.

The infrared irradiation time to the light emitting layer was 7 minutes. The rate of temperature rise in the firing of the light emitting layer was 80 DEG C / min for the initial 30 seconds. After heating, the temperature reached 70 캜 in 30 seconds. Therefore, the time t of 70 ° C or more was 6 minutes and 30 seconds. α / t was 0.018 μm ² / s.

(Comparative Example 12)

When the conditions for forming the hole injection layer of Example 16 were changed as described below, the hole injection layer was not insolubilized and an organic electroluminescent device could not be produced.

<Hole injection layer>

A composition for forming a hole injection layer of 2.5% by weight was prepared by using 100 parts by weight of the polymer compound represented by the formula (P4), 20 parts by weight of the compound represented by the formula (A1) and ethyl benzoate as a solvent.

This coating composition is spin-coated on the substrate. The number of revolutions of the spin coat is 1500 rpm, and the time is 30 seconds. After spin-coating, the solvent is dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the firing method of the hole injection layer is heated for 10 minutes by a hot air dryer at 230 占 폚.

(Comparative Example 13)

When the conditions for forming the hole injection layer of Example 18 were changed as described below, the hole injection layer was not insolubilized and an organic electroluminescent device could not be produced.

<Hole injection layer>

100 weight parts of the polymer compound represented by the above formula (P6), 20 weight parts of the compound represented by the above formula (A1), and ethyl benzoate as a solvent are used to prepare a composition for forming a hole injection layer of 3.5 weight%.

This coating composition is spin-coated on the substrate. The number of revolutions of the spin coat is 1500 rpm, and the time is 30 seconds. After spin-coating, the solvent is dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the firing method of the hole injection layer is heated for 10 minutes by a hot air dryer at 230 占 폚.

(Comparative Example 14)

When the conditions for forming the hole transporting layer of Example 18 were changed as described below, the hole transporting layer was not insolubilized and an organic electroluminescent device could not be produced.

&Lt; Hole transport layer &

A 2.5 wt% hole transporting layer coating liquid is prepared by using cyclohexylbenzene as the solvent of the high molecular material represented by the following formula (P5).

This coating composition is spin-coated on the substrate. The number of revolutions of the spin coat is 1500 rpm, and the time is 100 seconds. Thereafter, the solvent for 30 seconds is dried with a hot plate at 230 캜. Thereafter, the firing method of the hole injection layer is heated for 10 minutes by a hot air dryer at 230 占 폚.

Table 14 summarizes the characteristics of the devices obtained in the above examples. The voltage and current efficiencies are determined by a voltage relative value and a current efficiency relative to the organic electroluminescent element 12 divided by a voltage (V) and a current efficiency (cd / A) at 10 mA / Respectively.

As described above, when the hole injecting layer, the hole transporting layer, and the light emitting layer are formed under the conditions of Examples 16 to 21, lamination can be performed by firing each layer for a short time, and this can not be achieved by baking with a hot- A short tact time can be attained, and an organic electroluminescent device can be manufactured at low cost.

(Example 22)

An organic electroluminescent device 18 was obtained in the same manner as in Example 3 except that the conditions for forming the hole injecting layer, the hole transporting layer, and the light emitting layer were changed as follows.

<Hole injection layer>

A composition for forming a hole injection layer of 3.0 weight% was prepared using 100 parts by weight of the polymer compound represented by the following formula (P7), 15 parts by weight of the compound represented by the formula (A1) and ethyl benzoate as a solvent.

(57)

This coating composition was spin-coated on the substrate. The number of revolutions of the spin coat was 3500 rpm, and the time was 30 seconds. After spin-coating, the solvent was dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the periphery of the glass substrate was wiped with toluene.

For baking the hole injection layer, a ceramic coated infrared heater (manufactured by Ushio Inc., heater peak wavelength: 2.5 mu m) was used. The irradiation time of the infrared ray was set to 6 minutes. The time for reaching 70 占 폚 was 10 seconds after the infrared ray irradiation, and the time for reaching 150 占 폚 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 DEG C or more was 5 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.023 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 50 nm.

&Lt; Hole transport layer &

A 3.0 wt% hole transporting layer coating liquid was prepared by using cyclohexylbenzene as a solvent of a polymer material represented by the following formula (P8).

(58)

This positive hole transport layer coating liquid was spin-coated on the previously prepared positive hole injection layer under nitrogen. The film was formed at a spinning speed of 1500 rpm for 100 seconds. Thereafter, the solvent for 30 seconds was dried with a hot plate at 230 캜. Thereafter, the periphery of the substrate was wiped off with toluene.

The firing was carried out using the same infrared heater as in the formation of the hole injection layer. The irradiation time of the infrared ray was set to 6 minutes. The time for reaching 150 캜 was 50 seconds after the infrared irradiation. Therefore, the time of 150 DEG C or more was 5 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.023 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 40 nm.

<Light Emitting Layer>

25 parts by weight, 75 parts by weight, and 10 parts by weight of the compounds H3, H4 and D4 represented by the following formulas were respectively fed with 4.5 wt% of cyclohexylbenzene as a solvent. This luminescent layer coating liquid was spin-coated on the previously prepared hole transporting layer under nitrogen. The film was formed for 120 seconds at a spinning speed of 2400 rpm. Thereafter, the periphery of the substrate was wiped off with toluene. After the film formation, it was heated at 120 DEG C for 20 minutes by a hot plate under nitrogen. The film thickness at this time was 50 nm.

[Chemical Formula 59]

(Example 23)

An organic electroluminescent device 19 was obtained in the same manner as in Example 22 except that the conditions for forming the hole injection layer were changed as follows.

<Hole injection layer>

As the heating of the substrate, the irradiation time of the infrared ray was set to 15 minutes by using a halogen heater (manufactured by Ushio Inc., heater peak wavelength: 1.2 mu m). The time for reaching 70 占 폚 was 10 seconds after the infrared ray irradiation, and the time for reaching 150 占 폚 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 DEG C or more was 14 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.0040 占 퐉 ² / sec.

(Example 24)

An organic electroluminescent device 20 was obtained in the same manner as in Example 23 except that the conditions for forming the hole injection layer and the hole transport layer were changed as follows.

<Hole injection layer>

The irradiation time of the infrared ray was set to 10 minutes. The time for reaching 70 占 폚 was 10 seconds after the infrared ray irradiation, and the time for reaching 150 占 폚 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 ° C or more was 9 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.0061 占 퐉 ² / sec.

&Lt; Hole transport layer &

A 3.0 wt% hole transporting layer coating liquid was prepared by using cyclohexylbenzene as a solvent as a polymer material represented by the following formula (P9). This positive hole transport layer coating liquid was spin-coated on the previously prepared positive hole injection layer under nitrogen. The film was formed at a spinning speed of 1500 rpm for 100 seconds. Thereafter, the solvent for 30 seconds was dried with a hot plate at 230 캜. Thereafter, the periphery of the substrate was wiped off with toluene. The firing was carried out using the same halogen heater as the hole injection layer. The irradiation time of the infrared ray was set to 6 minutes. The time for reaching 150 캜 was 50 seconds after the infrared irradiation. Therefore, the time of 150 DEG C or more was 5 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.023 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 40 nm.

(60)

(Example 25)

An organic electroluminescent device 21 was obtained in the same manner as in Example 24 except that the conditions for forming the hole injection layer were changed as follows.

<Hole injection layer>

100 weight parts of the polymer compound represented by the following formula (P10), 15 weight parts of the compound represented by the formula (A1), and ethyl benzoate as a solvent were used to prepare a composition for forming a hole injection layer of 3.0 weight%.

(61)

This coating composition was spin-coated on the substrate. The number of revolutions of the spin coat was 3500 rpm, and the time was 30 seconds. After spin-coating, the solvent was dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the periphery of the glass substrate was wiped with toluene.

The firing of the hole injection layer was carried out using the same infrared heater as in Example 22. The irradiation time of the infrared ray was set to 6 minutes. The time for reaching 70 占 폚 was 10 seconds after the infrared ray irradiation, and the time for reaching 150 占 폚 was 50 seconds after the infrared ray irradiation. Therefore, the time of 150 DEG C or more was 5 minutes and 10 seconds. The maximum reachable temperature of the substrate was 270 ° C. ? / t was 0.023 占 퐉 ² / sec. The above process was carried out under the atmosphere. The film thickness was 50 nm.

(Comparative Example 15)

When the conditions for forming the hole injection layer of Example 23 were changed as described below, the hole injection layer was not insolubilized and an organic electroluminescent device could not be produced.

<Hole injection layer>

100 weight parts of the polymer compound represented by the formula (P7), 15 weight parts of the compound represented by the formula (A1), and ethyl benzoate as a solvent are used to prepare a composition for forming a hole injection layer of 3.0 weight%.

This coating composition is spin-coated on the substrate. The number of revolutions of the spin coat is 3500 rpm, and the time is 30 seconds. After spin-coating, the solvent is dried on a hot plate at 80 DEG C for 30 seconds. Thereafter, the firing method of the hole injection layer is heated for 15 minutes by a hot-air dryer at 230 占 폚.

(Comparative Example 16)

When the conditions for forming the hole transporting layer of Example 22 were changed as described below, the hole transporting layer was not insolubilized and an organic electroluminescent device could not be produced.

&Lt; Hole transport layer &

A 3.0 wt% hole transporting layer coating liquid is prepared by using cyclohexylbenzene as the solvent of the high molecular material represented by the above formula (P8).

This coating composition is spin-coated on the substrate. The number of revolutions of the spin coat is 1500 rpm, and the time is 100 seconds. Thereafter, the firing method of the hole transporting layer is heated for 6 minutes on a hot plate at 230 占 폚.

(Comparative Example 17)

The hole transport layer was not insolubilized even when a hole transport layer was formed in the same manner as in Comparative Example 16 except that the polymer material shown in the above formula (P9) was used instead of the polymer material represented by the above formula (P8) Could not be manufactured.

Table 15 summarizes the characteristics of the devices obtained in the above examples. The voltage and current efficiencies were represented by relative values of voltage and current efficiency divided by the voltage (V) and the current efficiency (cd / A) at 2500 cd / m 2 of the organic electroluminescent device 18.

Thus, when the hole injecting layer and the hole transporting layer are formed under the conditions of Examples 22 to 25, lamination can be performed by firing each layer for a short time, and a short-time Tact time can be achieved, and an organic electroluminescent device can be manufactured at a low cost.

Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is related to Japanese patent application (Japanese patent application 2012-121147) filed on May 28, 2012, Japanese patent application filed on June 27, 2012 (Japanese patent application 2012-144392) and August 21, 2012 (Japanese Patent Application No. 2012-182611), the content of which is incorporated herein by reference.

1: substrate
2: anode
3: Hole injection layer
4: hole transport layer
5: light emitting layer
6: hole blocking layer
7: Electron transport layer
8: electron injection layer
9: cathode

Claims (36)

A method for manufacturing a conductive thin film laminate comprising a substrate and an electrically conductive thin film formed on the substrate,
The conductive thin film is formed by applying a conductive thin film precursor containing a polymer compound having a repeating unit represented by the following formula (1) and having a crosslinking group on a substrate or on a conductive thin film formed on the substrate, Wherein the conductive thin film laminate is formed by crosslinking.
[Chemical Formula 1]

(In the formula (1), Ar ^a or Ar ^b each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group having 4 to 60 carbon atoms which may have a substituent.) The method according to claim 1,
Wherein the crosslinking group is a crosslinking group selected from the following &lt; crosslinking group T &gt;.
&Lt; Crosslinkable group T &
(2)

(Wherein R ²¹ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar ⁴¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. The butene ring may have a substituent.) 3. The method of claim 2,
Wherein the crosslinkable group is a benzocyclobutene ring represented by the following formula (3).
(3)

4. The method according to any one of claims 1 to 3,
Wherein the conductive thin film precursor contains a polymer compound containing a repeating unit represented by the following formula (2).
[Chemical Formula 4]

Ar ²¹ and Ar ²² each independently represent an aromatic hydrocarbon group which may have a direct bond or a substituent or an aromatic heterocyclic group which may have a substituent and Ar ²³ to Ar ²³ each independently represent an aromatic heterocyclic group which may have a substituent, Ar ²⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent and T ² represents a crosslinkable group. 5. The method according to any one of claims 1 to 4,
Wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (4).
[Chemical Formula 5]

(In the formula (4), Ar ₆ and Ar ₇ each independently represent a bivalent aromatic ring group which may have a substituent, Ar ₈ represents a aromatic ring group which may have a substituent, and R ₈ and R ₉ each independently A hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent group, R ₈ and R ₉ are bonded to each other to form a ring P represents an integer of 1 to 5). 6. The method according to any one of claims 1 to 5,
Wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (6).
[Chemical Formula 6]

(Formula (6) ^{of, Ar 31, Ar 33, Ar} 34 and Ar ³⁵ each independently represents a divalent aromatic heterocyclic ring which may contain a divalent aromatic hydrocarbon ring group or a substituent which may have a substituent, Ar ³² is An aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic ring which may have a substituent.
R ¹¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent and R ¹² to R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms An alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
R ¹² and R ¹³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ may combine with each other to form a ring. R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring.
l, m and n each independently represents an integer of 0 to 2.) 7. The method according to any one of claims 1 to 6,
The substrate has a minimum value of the infrared transmittance in a wavelength range of 2000 to 3300 nm,
Wherein a product (?) Of a wavelength in a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 占 퐉 ² or more and 16 占 퐉 ² or less. 8. The method according to any one of claims 1 to 7,
Wherein a minimum value of the infrared transmittance of the substrate is 95% or less. 9. The method according to any one of claims 1 to 8,
Wherein a peak wavelength of an infrared ray is 0.8 占 퐉 or more and 25 占 퐉 or less. 10. The method according to any one of claims 1 to 9,
Wherein the conductive thin film precursor is heated at a temperature of 150 占 폚 or higher and 300 占 폚 or lower when the temperature of the substrate is irradiated with infrared rays and the holding time in the temperature range is 5 seconds or more and 30 minutes or less. 11. The method according to any one of claims 1 to 10,
Wherein the conductive thin film precursor is heated at a temperature of 150 ° C or higher and 300 ° C or lower when the temperature of the substrate is irradiated with infrared rays and the period of time at which the conductive thin film precursor is maintained at a constant temperature in the temperature range is 20 seconds or more and 15 minutes or less Gt; 12. The method according to any one of claims 1 to 11,
Wherein the substrate is heated by infrared rays at a temperature raising rate of not less than 10 占 폚 / min and not more than 250 占 폚 / min. 13. The method according to any one of claims 1 to 12,
When the product of the wavelength at the minimum value of the infrared transmittance of the substrate and the peak wavelength of the infrared ray and the holding time t (seconds) at the temperature of the substrate of 150 DEG C or higher satisfy the following relationship (7) Of the conductive thin film laminate.
0.002?? / T (? ² / s)? 0.2 (7) 1. A method for producing a conductive thin film laminate comprising a substrate and a conductive thin film formed on the substrate, wherein the film thickness is 50 nm or more and 1 m or less,
The conductive thin film is formed by applying a conductive thin film precursor containing a polymer compound having a repeating unit represented by the following formula (1) and having a crosslinking group on a substrate or on a conductive thin film formed on the substrate, Wherein the conductive thin film laminate is formed by crosslinking.
(7)

(In the formula (1), Ar ^a or Ar ^b each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group having 4 to 60 carbon atoms which may have a substituent.) 15. The method of claim 14,
Wherein the crosslinking group is a crosslinking group selected from the following &lt; crosslinking group T &gt;.
&Lt; Crosslinkable group T &
[Chemical Formula 8]

(Wherein R ²¹ to R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar ⁴¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. The butene ring may have a substituent.) 16. The method of claim 15,
Wherein the crosslinkable group is a benzocyclobutene ring represented by the following formula (3).
[Chemical Formula 9]

17. The method according to any one of claims 14 to 16,
Wherein the conductive thin film precursor contains a polymer compound containing a repeating unit represented by the following formula (2).
[Chemical formula 10]

Ar ²¹ and Ar ²² each independently represent an aromatic hydrocarbon group which may have a direct bond or a substituent or an aromatic heterocyclic group which may have a substituent and Ar ²³ to Ar ²³ each independently represent an aromatic heterocyclic group which may have a substituent, Ar ²⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent and T ² represents a crosslinkable group. 18. The method according to any one of claims 14 to 17,
Wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (4).
(11)

(In the formula (4), Ar ₆ and Ar ₇ each independently represent a bivalent aromatic ring group which may have a substituent, Ar ₈ represents a aromatic ring group which may have a substituent, and R ₈ and R ₉ each independently A hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent group, R ₈ and R ₉ are bonded to each other to form a ring P represents an integer of 1 to 5). 19. The method according to any one of claims 14 to 18,
Wherein the conductive thin film precursor contains a polymer compound having a partial structure represented by the following formula (6).
[Chemical Formula 12]

(Formula (6) ^{of, Ar 31, Ar 33, Ar} 34 and Ar ³⁵ each independently represents a divalent aromatic heterocyclic ring which may contain a divalent aromatic hydrocarbon ring group or a substituent which may have a substituent, Ar ³² is An aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic ring which may have a substituent.
R ¹¹ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent and R ¹² to R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms An alkoxy group having 1 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
R ¹² and R ¹³ may combine with each other to form a ring. R ¹⁴ and R ¹⁵ may combine with each other to form a ring. R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring.
l, m and n each independently represents an integer of 0 to 2.) 20. The method according to any one of claims 14 to 19,
The substrate has a minimum value of the infrared transmittance in a wavelength range of 2000 to 3300 nm,
Wherein a product (?) Of a wavelength in a minimum value of the infrared transmittance and a peak wavelength of the infrared ray is 2 占 퐉 ² or more and 16 占 퐉 ² or less. 21. The method according to any one of claims 14 to 20,
Wherein a minimum value of the infrared transmittance of the substrate is 95% or less. 22. The method according to any one of claims 14 to 21,
Wherein a peak wavelength of an infrared ray is 0.8 占 퐉 or more and 25 占 퐉 or less. 23. The method according to any one of claims 14 to 22,
Wherein the conductive thin film precursor is a conductive thin film laminate having a substrate heated at a temperature of not less than 70 ° C. and not more than 300 ° C. at the time of infrared irradiation, Way. 24. The method according to any one of claims 14 to 23,
Wherein the conductive thin film precursor is a conductive thin film laminated with a substrate heated at a temperature of not less than 70 ° C. and not more than 300 ° C. at the time of irradiation with infrared rays and having a time at which the substrate is maintained at a constant temperature in the temperature range of not less than 20 seconds and not more than 15 minutes &Lt; / RTI &gt; 25. The method according to any one of claims 14 to 24,
Wherein the substrate is heated by infrared rays at a temperature raising rate of not less than 10 占 폚 / min and not more than 250 占 폚 / min. 26. The method according to any one of claims 14 to 25,
(7), when a product (?) Of a wavelength at a minimum value of the infrared ray transmittance of the substrate and a peak wavelength of the infrared ray and a time (t: &Lt; / RTI &gt;
0.002?? / T (? ² / s)? 0.2 (7) A method of manufacturing a conductive thin film laminate including a substrate and a conductive thin film formed on the substrate,
The conductive thin film precursor contains a light emitting material,
Applying an ink containing the light emitting material and a solvent on a substrate or on a conductive thin film formed on the substrate and then heating the substrate at a temperature of 150 DEG C or less by infrared rays,
Wherein the temperature of the substrate is maintained for at least 5 seconds and not more than 20 minutes in a state of 70 占 폚 or more and 150 占 폚 or less under infrared irradiation. 28. The method of claim 27,
Wherein the conductive thin film precursor is heated at a temperature of 70 ° C or higher and 150 ° C or lower when the substrate is irradiated with infrared rays and a time period during which the substrate is maintained at a constant temperature in the temperature range is 20 seconds or longer and 10 minutes or shorter Gt; 29. The method of claim 27 or 28,
Wherein the substrate is heated by infrared rays at a temperature raising rate of not less than 10 占 폚 / min and not more than 250 占 폚 / min. 30. The method according to any one of claims 27 to 29,
Wherein the difference (? T = t1 - t2) between the boiling point (t1) of the solvent contained in the ink and the maximum temperature (t2) of the substrate temperature is not less than 5 占 폚. 32. The method according to any one of claims 27 to 30,
Wherein the boiling point of the solvent contained in the ink is not less than 75 占 폚 and not more than 350 占 폚. 32. The method according to any one of claims 27 to 31,
(?) Of a wavelength at a minimum value of the infrared transmittance of the substrate and a peak wavelength of the infrared ray, and a holding time t (seconds) at a temperature of the substrate of 70 ° C or higher, Wherein the conductive thin film layered body satisfies the following relationship.
0.003?? / T (? ² / s)? 0.5 (8) 32. A conductive thin film laminate obtained by the method according to any one of claims 1 to 32. 32. An organic electroluminescent device comprising the conductive thin film laminate according to claim 33. An organic EL display comprising the organic electroluminescent device according to claim 34. 34. An organic EL illumination device comprising the organic electroluminescence device according to claim 34.

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