JP2009146696A - Composition for forming outer edge prescribing film, manufacturing method of functional film, organic electroluminescent device, its manufacturing method, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material and a process for eliminating a complicated and constrained process on patterning a functional film, and for specifying the position of the outer edge in the patterned functional film at a low cost with a simple configuration, and further to provide the organic electroluminescent element of high capability using these material and process at a low cost. <P>SOLUTION: The composition for forming the outer edge specifying film is formed in the adjoining position to the functional film to constitute the outer edge of the functional film, wherein the composition includes a surfactant and a solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition for defining the position of an outer edge portion of a functional film, and more particularly to a composition for defining the position of an outer edge portion of an organic layer of an organic electroluminescent element.

  The process of forming a film having various functions such as optical and electrical on the surface of a substrate has become an important elemental technology that supports the realization of many devices today. These functional films are designed to appropriately express their functions by being arranged with a predetermined accuracy at a predetermined position on the surface of the substrate.

  As a patterning method for arranging a film at a predetermined position, a photolithography technique including an exposure / development process using a mask and a resist is widely used because of its high accuracy and reliability. However, in the photolithography technique, many methods for patterning a functional film directly on a substrate have been proposed and implemented from the viewpoint of cost increase caused by expensive introduction apparatuses and complicated processes.

  As a method for directly patterning the substrate surface, a relief printing using a plate, a gravure printing, a screen printing using a mask, a spray coating, and a method using an ink jet apparatus are being studied.

However, the method of directly printing and applying the functional film described above tends to have a low position accuracy of the pattern outer edge. That is, bleeding (spreading of the liquid spreads outside the pattern) occurs at the pattern edge, the pattern shape accuracy decreases, and film thickness unevenness occurs near the pattern edge.
One possible cause is the flow induced as the film formed on the substrate progresses. This flow is said to be one of the major causes of Marangoni flow caused by non-uniform surface tension generated on the film surface during drying.
In addition, setting the surface tension of the coating solution for forming a film low for the purpose of uniform adhesion of the film on the substrate is a cause of fluidization and bleeding.

  As a method that can be used to suppress the flow of such a film and increase the position accuracy of the outer edge of the pattern, there is a method in which a lyophobic part or a lyophilic part is formed in advance on the substrate in accordance with the film formation pattern. It has been published.

  For example, a method (Patent Document 1) is disclosed in which a functional film pattern is formed in accordance with a liquid repellent treatment pattern by making a region where a functional film is not formed lyophobic.

  On the other hand, as a method for defining the outer edge portion of the coating pattern of the electroluminescent layer, which is a functional film, a method (Patent Document 2) in which an electroluminescent layer forming liquid and a separating liquid are simultaneously applied is disclosed.

JP 2005-149767 A JP 2001-267068 A

However, in the method disclosed in Patent Document 1, it is necessary to perform a liquid repellent treatment on the region other than the region where the functional film is formed, and the cost tends to increase because the processing mechanism becomes large and the processing time increases.
In addition, as one of the substrate processing processes exemplified in Patent Document 1, there are surface treatment using a mask and application of a liquid repellent material, but the position and shape accuracy of the liquid repellent pattern edge itself are guaranteed. Therefore, it is not expected to improve the position accuracy of the pattern outer edge portion of the functional film to be subsequently formed.

  Furthermore, in the method of Patent Document 2, it is necessary that the electroluminescent layer forming liquid and the separating liquid are not mixed, and the kind of the separating liquid is remarkably limited. Moreover, it is also necessary to apply at the same time, and the application nozzle mechanism tends to be complicated.

  The present invention has been made in view of the above problems, and its purpose is to reduce the complexity and restrictions of the process when patterning the functional film, and to position the outer edge of the functional film to be patterned. It is to provide a material and a process for simply and simply defining the cost, and further to provide a low-cost and high-performance organic electroluminescence device using them.

  As a result of intensive studies by the present inventors, when a functional material is applied to a pattern on a substrate, if a solution containing a surfactant is applied to the outer edge of the pattern, bleeding at the edge of the applied pattern may occur. It was found that the pattern shape was suppressed and the present invention was completed.

  That is, the gist of the present invention is a composition that is formed adjacent to a functional film and forms an outer edge defining film that defines the outer edge of the functional film, and includes a surfactant and a solvent. In the composition for forming an outer edge regulating film (claim 1).

  At this time, it is preferable that the contact angle of the composition for forming an outer edge regulating film to the glass substrate is 18 ° or more (Claim 2).

  The outer edge regulating film forming composition preferably contains 0.001% by weight or more and 0.1% by weight or less of the surfactant.

  Furthermore, it is preferable that the surfactant is a fluorine-based surfactant or a silicone-based surfactant.

  Moreover, it is preferable that this composition for outer edge regulation film | membrane formation contains the material contained in this functional film (Claim 5).

  The functional film is preferably an organic layer of an organic electroluminescence device (Claim 6), and the organic layer is preferably a hole injection layer (Claim 7).

  Another gist of the present invention is characterized in that an outer edge defining film is formed on a base material using the above-described outer edge defining film forming composition, and then a functional film is formed adjacent to the outer edge defining film. The functional film manufacturing method (claim 8).

  Another gist of the present invention is characterized in that an outer edge defining film is formed on a substrate using the above-mentioned composition for forming an outer edge defining film, and then an organic layer is formed adjacent to the outer edge defining film. The present invention resides in a method for manufacturing an organic electroluminescent element.

  In this case, in the method for manufacturing an organic electroluminescent element, it is preferable that the organic layer is formed after the outer edge defining film is formed and before the outer edge defining film is dried (claim 10). A hole injection layer is preferred (claim 11).

Moreover, it is also preferable that this hole injection layer contains the polymer containing the repeating unit represented by following formula (1) (Claim 12).

  Another gist of the present invention is an organic electroluminescent device comprising an outer edge defining film containing a surfactant and an organic layer formed adjacent to the outer edge defining film on a substrate. (Claim 13).

  At this time, the outer edge defining film is preferably a film formed using the above-described outer edge defining film forming composition (Claim 14), and the organic layer is preferably a hole injection layer. (Claim 15).

  Another gist of the present invention resides in an image display device characterized in that the organic electroluminescent elements are assembled to display an image.

  When applying a pattern to the functional material on the substrate, by applying the outer edge regulating film forming composition containing a surfactant outside the pattern boundary, bleeding at the outer edge of the coating pattern is suppressed, A stable pattern shape can be obtained.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the examples described below, and can be implemented with various modifications within the scope of the gist thereof.

  The present invention relates to a composition for forming an outer edge defining film which is formed adjacent to a functional film and which defines the outer edge of the functional film, comprising a surfactant and a solvent. The present invention relates to a film forming composition. The present invention also relates to a method for producing a functional film, an organic electroluminescent element, a method for producing the same, and an image display device using the outer edge defining film forming composition.

  By using the composition for forming an outer edge defining film of the present invention, the position accuracy of the pattern outer edge portion of the functional film can be improved. Hereinafter, after describing the composition for forming an outer edge defining film, a functional film formed using the composition, a method for forming the functional film, an organic electroluminescent element having the functional film, and an image display device will be described.

  In the present invention, the “base material” refers to an object on which the outer edge defining film and the functional film are formed. On the other hand, the “substrate” refers to a component that serves as a basis for forming an organic electroluminescent element. For example, in the method for manufacturing an organic electroluminescent element of the present invention, a substrate may be selected as the base material, or a structure on the substrate may be selected. In the latter case, the outer edge defining film and the functional film are formed on the structure. Details of the organic electroluminescent device will be described later.

In the present invention, the “pattern” refers to a region designed to form a functional film. The outside of this area is called “pattern outside”, and the boundary between the pattern and the outside of the pattern is called “pattern boundary”.
The “pattern outer edge portion” refers to a portion near the pattern boundary of the pattern, and particularly refers to a portion in contact with the pattern boundary.
“Outside pattern boundary” refers to the outside of the pattern adjacent to the pattern boundary, and particularly refers to a portion in contact with the pattern boundary.
These will be described with reference to FIG. 5. Assuming that the functional film is designed to be formed in a region surrounded by a solid line, a “pattern” is a region represented by reference numeral 100 in a part surrounded by a solid line. The “outside pattern” is an area represented by the reference numeral 103 outside the portion 100 surrounded by a solid line, and the “pattern boundary” indicates a boundary line written by a solid line. The “pattern outer edge portion” refers to a portion of the pattern 100 particularly represented by reference numeral 101, and the “outside of the pattern boundary” refers to a portion of the pattern outer portion 103 particularly represented by reference numeral 102.

[1. Composition for forming outer edge regulating film]
The outer edge defining film refers to a film that is provided adjacent to the functional film to prevent the outer edge of the functional film from bleeding (spreading outside the pattern) and to define the position of the outer edge of the functional film.
When the functional film is simply formed by coating, bleeding tends to occur with the progress of drying after coating. Due to this bleeding, the accuracy of the pattern shape decreases. Further, the thickness of the blurred portion is not constant as compared with the portion formed in the original pattern, and the film thickness tends to be uneven near the pattern edge. When unevenness of the film thickness occurs, for example, when the functional film is a conductor, the conductivity is different, and when the functional film is a light emitting layer of an organic electroluminescent element, the intensity of light emission is different. The quality of the functional film tends to be lowered.

  The composition for forming an outer edge regulating film of the present invention is a composition containing a surfactant and a solvent. Before forming a functional film, the composition is applied to the outer edge of the pattern to form an outer edge regulating film. By forming, bleeding of the functional film can be prevented. Hereinafter, the composition for forming an outer edge regulating film will be described.

(Surfactant)
The outer edge regulating film forming composition of the present invention contains a surfactant. The surfactant referred to in the present invention refers to a molecule having a lipophilic group (low polarity) and a hydrophilic group (high polarity).

As the surfactant, any known surfactant can be used as long as the compound meets the above definition. Specific examples include fluorine-based surfactants whose lipophilic group is a fluorocarbon group, silicone-based surfactants whose lipophilic group is a siloxane chain, surfactants whose lipophilic group is an alkyl group, and the like. Of these, fluorine surfactants (especially those containing perfluoroalkyl groups) and silicone surfactants (especially those containing siloxane bonds) are preferred, and fluorine surfactants (especially those containing perfluoroalkyl groups). Are particularly preferred.
The hydrophilic group of these surfactants is preferably, for example, a hydroxyl group, a carbonyl group, a carboxyl group or the like. Polyether, polyglycerin and the like are also preferable.
One of these surfactants may be used alone, or two or more thereof may be used in any combination and ratio.

(solvent)
The solvent contained in the composition for forming an outer edge regulating film is not limited as long as the above-described surfactant can be dissolved. Among these, from the viewpoint of workability when applying the outer edge regulating film forming composition, it is preferable that the volatilization rate is not extremely fast or slow. Moreover, it is preferable not to corrode a base material and the structure formed in the surface.

  Examples of such a solvent include hydrocarbons, alcohols, ethers, ketones, esters and the like.

  Examples of the hydrocarbon include toluene, xylene, ethylbenzene, trimethylbenzene, tetralin, butylbenzene, cyclohexylbenzene, and the like.

  Examples of the alcohol include ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, amyl alcohol, hexyl alcohol, benzyl alcohol, and cyclohexanol.

  Examples of the ether include dibutyl ether, dihexyl ether, anisole, phenetole, butyl phenyl ether, methyl anisole, ethyl benzyl ether, diphenyl ether, dimethoxybenzene, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Examples include butyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

  Examples of the ketone include methyl ethyl ketone, methyl propyl ketone, diethyl ketone, butyl methyl ketone, methyl pentyl ketone, dipropyl ketone, isophorone, cyclohexanone, and methyl phenyl ketone.

  Examples of the ester include ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, methoxybutyl acetate, ethyl butyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl benzoate, and ethyl benzoate. , Propyl benzoate, butyl benzoate, γ-butyrolactone, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Is mentioned.

  Moreover, it is preferable that at least 1 type of the solvent used for the composition for outer edge regulation film | membrane formation is the same as at least 1 type among the solvents used for forming a functional film. This is because the outer edge defining film can be formed by the same method as the functional film forming method, and the outer edge defining film can be simultaneously dried in the process of drying the functional film.

  In addition, these solvents may be used alone or in combinations of two or more in any ratio.

  The boiling point of the solvent is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Below this range, the workability of coating formation may be reduced due to high volatility. Further, if it exceeds this range, it is necessary to raise the temperature for drying, and the functional film tends to be easily denatured.

(Other contents)
The composition for forming an outer edge regulating film of the present invention may contain other compounds in addition to the surfactant and the solvent as long as the effects of the present invention are not significantly impaired. For example, a material contained in the functional film may be included. This is because, even when the functional film is applied and formed, even when it contacts and mixes with the outer edge regulating film forming composition, the change in the composition of the outer edge of the functional film can be reduced and the quality of the functional film can be maintained. The materials contained in the functional film are exemplified as the functional film materials below.

  Moreover, in order to make it easy to confirm the formation of the outer edge regulating film, a pigment or the like may be contained.

(Physical properties of the outer edge regulating film forming composition)
The content of the surfactant in the composition for forming the outer edge regulating film is usually 0.001% by weight or more, preferably 0.002% by weight or more, more preferably 0.005% by weight or more, and usually 0.1% by weight. % Or less, preferably 0.05% by weight or less, more preferably 0.02% by weight or less.
Outside this range, the amount of surfactant on the surface of the outer edge defining film becomes excessive or insufficient, and the composition for forming the outer edge defining film tends to bleed. Therefore, the positional accuracy of the outer edge defining film is lowered, and there is a possibility that the positional accuracy of the functional film is also lowered.

  The contact angle of the composition for forming an outer edge regulating film on the glass substrate is usually 18 ° or more, preferably 25 ° or more, more preferably 30 ° or more, and usually 60 ° or less. The higher this value, the higher the positional accuracy when applying the outer edge defining film forming composition, thereby reducing the bleeding of the functional film.

  Here, the contact angle to the glass substrate means that 0.3 μL of the composition for forming an outer edge regulating film is applied to a glass substrate (a sheet glass of borosilicate (crown) glass), and the composition and the glass substrate It is the value which measured the contact angle using the contact angle measuring apparatus (Kyowa Interface Science Co., Ltd. product (CA-DT type | mold)).

[2. Functional membrane]
The functional film according to the present invention includes, for example, an energy conversion film (photoelectric conversion film, electroluminescent film), a charge conduction / insulation film (electrode, hole transport layer, charge injection layer, electrical insulation film, electrical resistance film), An optical film (a deflection filter film, a color filter film, a light blocking film (mask)), a protective film, a smoothing film, an adhesive film, or the like is intended to express a specific function.

The functional film according to the present invention is characterized by being formed adjacent to the outer edge defining film after the outer edge defining film is formed using the outer edge defining film forming composition of the present invention. Therefore, the material of the functional film is not limited as long as it is a material for expressing the target function or a material for maintaining the shape of the functional film and can be easily dissolved or dispersed in an organic solvent or water. There is no.
Hereinafter, the functional film will be described.

(material)
The functional film according to the present invention is a general term for films having various functions as described above. Accordingly, examples of the material include a charge transport material, a charge generation material, an electroluminescent material, an electrically insulating material, a polarizing material, and a binder material according to the purpose.
Further, when classified by the form of the material, organic polymer materials, organic low molecular materials, organic pigments, inorganic pigments, organic dyes, inorganic dyes, inorganic particles, and the like can be given.

  Among these, the functional film according to the present invention is preferably an organic layer of an organic electroluminescent element. Among these, a hole injection layer is preferable. The material of the organic layer of the organic electroluminescent element will be described later.

(solvent)
As described above, the functional film material is a material that is easily dissolved or dispersed in a solvent (organic solvent or water).
Here, as an organic solvent, [1. The solvent described in (solvent) of the outer edge regulating film forming composition] is preferable. Moreover, it is preferable that at least one of the solvents used for forming the functional film is the same as at least one of the solvents used in the outer edge defining film forming composition.
One of these solvents may be used alone, or two or more thereof may be used in any combination and ratio.

(Other contents)
The functional film according to the present invention may contain any compound as long as the effects of the present invention are not significantly impaired. For example, an antioxidant or a dispersion aid can be mixed. The stability of the material forming the functional film can be maintained.
There is no limitation on the method of mixing these compounds, and the functional film may be impregnated in the functional film after coating formation, or may be contained in a solution or dispersion of the functional film material for coating formation.

(Content rate of functional membrane materials)
In a functional film material solution or dispersion (hereinafter sometimes referred to as “functional film-forming composition” as appropriate), the functional film material content depends on the desired functional film thickness. For example, when the functional film is a thin film having a thickness of 1 μm or less, it is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less. As the desired thickness of the functional film increases and the content rate increases, the film can be formed more efficiently. The upper limit of the content is usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less. What is necessary is just to determine by the range of the content rate suitable for the solubility to the solvent of the material of a functional film, and the kind of method of application | coating formation.

(Physical properties of functional film forming composition)
The composition for forming a functional film according to the present invention is preferably difficult to mix with the composition for forming an outer edge defining film. Specifically, when 0.5 μL (microliter) of the functional film forming composition and 0.5 μL of the outer edge regulating film forming composition are dropped onto the glass substrate at intervals of 2 mm, the compositions of each other are formed. The time for not mixing is usually 1 minute or longer, preferably 3 minutes or longer, particularly preferably 10 minutes or longer. This is because, when mixed easily, a composition change occurs due to mixing with the outer edge defining film forming composition at the outer edge portion of the functional film, and it tends to be difficult to obtain a homogeneous functional film.

[3. Functional membrane production method]
According to the method for forming a functional film of the present invention, an outer edge defining film is formed on a substrate using the outer edge defining film forming composition of the present invention, and then a functional film is formed adjacent to the outer edge defining film. It is characterized by. At this time, it is also preferable that the functional film is an organic layer.
Hereafter, the manufacturing method of the functional film of this invention is demonstrated.

(Formation of outer edge regulation film)
The outer edge defining film is formed by applying the outer edge defining film forming composition so as to be adjacent to the pattern outside the pattern of the functional layer.
The coating method is not limited as long as the effects of the present invention are not significantly impaired. For example, the spray coating method, the ink jet method, the screen printing method, the flexographic printing method, the nozzle printing method, the offset printing method, the aerosol method, the aerosol jet method, and the like may be any of contact coating and non-contact coating as long as patterning is possible.
In addition, one of these methods may be performed alone, or two or more may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

You may dry after application | coating of the composition for outer edge regulation film formation, and before formation of a functional film.
Examples of the drying method include vacuum drying, hot air drying, infrared drying, hot plate drying, and the like.
In addition, one of these methods may be performed alone, or two or more may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

  When the functional material is formed, the outer edge regulating film forming composition may be completely dried, may not be completely dried, or may not be dried. However, depending on the type of the surfactant, if the drying is not completed or is not performed, the stability of the outer edge regulating film forming composition may be lowered. Therefore, the dry state may be appropriately selected depending on the composition of the outer edge regulating film forming composition.

When drying is not completed or when drying is not performed, the thickness of the outer edge regulating film is usually 1 μm or more, preferably 5 μm or more, and usually 500 μm or less, preferably 200 μm or less. Below this range, the outer edge defining membrane may become discontinuous. On the other hand, if it exceeds this range, the area of the outer edge defining film may increase, which may hinder the arrangement of other functional films.
Further, the thickness of the outer edge regulating film that has been completely dried is usually 100 μm or less, preferably 20 μm or less. If it exceeds this range, the thickness of the element including the functional film may be increased.

(Formation of functional film)
After forming the outer edge defining film, a functional film is formed in a pattern bordered by the outer edge defining film. In the case of forming an organic film, the organic film material is used among the functional film materials described above.
The functional film is preferably formed by a coating method, and preferably formed by non-contact coating with a substrate such as a spray coating method, an ink jet method, a nozzle printing method, an aerosol method, an aerosol jet method or the like. Of these, the inkjet method, the nozzle printing method, and the aerosol jet method are preferable. This is because a coating pattern can be formed by positioning without using a mask.
In addition, one of these methods may be performed alone, or two or more may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

When the functional film is formed by a coating method, it is preferable to perform drying. Examples of the drying method include vacuum drying, hot air drying, infrared drying, and hot plate drying.
In addition, one of these methods may be performed alone, or two or more may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

  However, depending on the type of the functional film formed, it may be transformed at the temperature used for drying. In this case, it is preferable to select a drying method that is performed without heating, to select natural drying, or to dry at a temperature that does not change.

[4. Organic electroluminescent device and method for producing the same]
The organic electroluminescent element of the present invention is characterized by having, on a base material, an outer edge defining film containing a surfactant and an organic layer formed adjacent to the outer edge defining film. At this time, it is preferable that the outer edge regulating film is formed using the outer edge regulating film forming composition of the present invention.

  The organic electroluminescent element of the present invention is not limited as long as it has the above-described characteristics, as long as the effects of the present invention are not significantly impaired, and the structure, layer structure, size, etc. thereof are any known form. You may have. In other words, the organic electroluminescent element may be configured to have a light emitting layer between at least two electrodes, and may have other layers such as a hole injection layer depending on the design of the organic electroluminescent element. Good. In addition, a configuration in which two or more organic electroluminescent elements share a part of the layer (for example, light emission for each section of the organic electroluminescent element on a laminate of one substrate, an electrode, and a hole injection layer) A structure in which layers and the like are formed).

  In the present invention, as an example of the above-described organic electroluminescent element, the organic electroluminescent element represented in the drawing will be described with reference to the schematic diagrams of FIGS.

FIG. 1 is a cross-sectional view schematically showing the structure of the organic electroluminescent element in the embodiment. An organic electroluminescent element 10 a shown in FIG. 1 has an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 6 on a substrate 1.
The organic layer of the organic electroluminescent element of the present invention may be any layer as long as it is an organic layer of a known organic electroluminescent element, but is preferably a hole injection layer.
In the following, the method for producing the organic electroluminescent element of the present invention is described first, and then each of the above layers is described.

<4-1. Manufacturing method of organic electroluminescent element of the present invention>
In the method for producing an organic electroluminescent element of the present invention, an outer edge defining film is formed on a substrate using the outer edge defining film forming composition of the present invention, and then an organic layer is formed adjacent to the outer edge defining film. It is characterized by doing. The organic layer may be at least one of the organic layers of the organic electroluminescent element, may be two or more layers, or may be all organic layers. However, among these, the organic layer is preferably a hole injection layer. The hole injection layer often has an area including a plurality of organic electroluminescent elements as its formation pattern. Therefore, the shape of the pattern boundary is simple and the length is not as large as the outer peripheral length of the substrate. This is because a sufficient effect can be obtained even though the formation of the film is easy.

  For example, when the organic layer is the hole injection layer 3 of the organic electroluminescence device of FIG. 1, the present invention is provided outside the pattern boundary of the hole injection layer 3 on the base material (that is, the anode 2). The outer edge regulating film forming composition is applied to form an outer edge regulating film.

(Formation of outer edge regulation film)
As a method for applying the outer edge regulating film forming composition, [3. Any of the methods described in “Method for producing functional film” may be used. However, when manufacturing an organic electroluminescent element, an inkjet method, an offset printing method, and an aerosol jet method are preferable. As a coating method, one type may be performed alone, or two or more types may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

You may dry after application | coating of the composition for outer edge regulation film formation, and before formation of an organic layer (in the above-mentioned example, hole injection layer 3).
As a drying method, [3. Any of the methods described in “Method for producing functional film” may be used.
As a coating method, one type may be performed alone, or two or more types may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

  When the organic layer (in the above example, the hole injection layer 3) is formed, the outer edge regulating film forming composition may be completely dried or may not be completely dried. It does not have to be dry. In particular, it is preferable to form the organic layer before the outer edge regulating film is dried. Therefore, the organic layer can be applied immediately after the outer edge regulating film is applied without passing through a drying process, thereby simplifying the manufacturing process. In addition, since an effect can be obtained even if a part of the outer edge defining film is dried during the process of applying the organic layer, a special means for controlling the drying rate of the outer edge defining film may not be used.

When drying is not completed or when drying is not performed, the thickness of the outer edge regulating film is usually 1 μm or more, preferably 5 μm or more, and usually 500 μm or less, preferably 200 μm or less. Below this range, the outer edge defining membrane may become discontinuous. On the other hand, if it exceeds this range, the area of the outer edge defining film increases, which may hinder the arrangement of other organic films.
Further, the thickness of the outer edge regulating film that has been completely dried is usually 20 μm or less, preferably 5 μm or less. Beyond this range, there is a possibility that the arrangement of other structures (electrodes, etc.) of the organic electroluminescent device will be an obstacle.

(Formation of organic layer)
An organic layer (in the above example, hole injection layer 3) is formed in the pattern bordered by the outer edge defining film. The functional film is preferably formed by a coating method. Specifically, [3. Any of the methods described in “Method for producing functional film” may be used. However, when manufacturing an organic electroluminescent element, an inkjet method, a nozzle printing method, and an aerosol jet method are preferable. As a coating method, one type may be performed alone, or two or more types may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

When the functional film is formed by a coating method, it is preferable to perform drying. As a drying method, [3. Any of the methods described in “Method for producing functional film” may be used.
As a drying method, one type may be performed alone, or two or more types may be performed in any combination. In the case of two or more types, they may be performed simultaneously or sequentially.

  However, depending on the type of the functional film formed, it may be transformed at the temperature used for drying. In this case, it is preferable to select a drying method that is performed without heating, to select natural drying, or to dry at a temperature that does not change.

<4-2. Substrate>
The substrate 1 serves as a support for the organic electroluminescent element 10a, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, it is preferable to use a transparent substrate made of a general-purpose material such as a glass plate, a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone.

  Examples of the material of the substrate 1 include various types of shot glass such as BK7, SF11, LaSFN9, BaK1, and F2, synthetic phased silica glass, optical crown glass, low expansion borosilicate glass, sapphire glass, soda glass, and alkali-free glass. Glass, TFT-formed glass, and polymer materials include acrylic resins such as polymethylmethacrylate and cross-linked acrylate, aromatic polycarbonate resins such as bisphenol A polycarbonate, polyester resins such as polyethylene terephthalate, and polycycloolefins. Examples thereof include crystalline polyolefin resins, epoxy resins, styrene resins such as polystyrene, polysulfone resins such as polyethersulfone, and synthetic resins such as polyetherimide resin. Moreover, 2 or more types of laminated bodies may be sufficient among these. Depending on the purpose and application, an optical film such as an antireflection film, a circularly polarizing film, or a retardation film may be formed on or bonded to these substrates.

  However, it is preferable to pay attention to gas barrier properties when using a synthetic resin substrate. This is because if the gas barrier property of the substrate 1 is too small, the organic electroluminescent element 10a may be deteriorated by the outside air that has passed through the substrate 1. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.

<4-3. Anode>
On the substrate 1, for example, an anode 2 is provided. The anode 2 plays the role of hole injection into the light emitting layer 5 side.
This anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; a carbon black, or It is composed of a conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline. In addition, only 1 type may be used for the material of the anode 2, and 2 or more types may be used together by arbitrary combinations and a ratio.

Although there is no restriction | limiting in the formation method of the anode 2, Usually, it carries out by sputtering method, a vapor deposition method, etc. In addition, when forming the anode 2 using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, an appropriate binder resin solution is used. The anode 2 can also be formed by dispersing them and applying them onto the substrate 1. Furthermore, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett. 60, 2711, 1992).
In addition, the anode 2 is usually a single layer structure, but may be a laminated structure made of a plurality of materials if desired.

  The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more. Also, it is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when the anode 2 may be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Further, it is possible to laminate different conductive materials on the anode 2.

Further, for the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property, the surface of the anode 2 is subjected to ultraviolet (UV) / ozone treatment, oxygen plasma, argon plasma. It is preferable to process.
Further, for the purpose of further improving the efficiency of hole injection and improving the adhesion of the hole injection layer 3 to the anode 2, a known anode buffer layer is provided between the hole injection layer 3 and the anode 2. It may be inserted.

<4-4. Hole injection layer>
The hole injection layer 3 is a layer that transports holes from the anode 2 to the light emitting layer 5 side. Hereinafter, components contained in the hole injection layer 3 will be described first, and then a method for forming the hole injection layer 3 will be described.

[4-4-1. (Material for hole injection layer)
The material of the hole injection layer 3 is not particularly limited as long as it can inject holes. When the hole injection layer 3 is formed by a wet film formation method, after forming the outer edge defining film using the outer edge defining film forming composition of the present invention, the hole injecting layer is adjacent to the outer edge defining film. It is preferable to form using a coating composition for a hole injection layer containing the above material (hereinafter also referred to as “hole injection layer composition” as appropriate). The material of the hole injection layer is not particularly limited as long as it can form the hole injection layer 3. Usually, as a material for the hole injection layer 3, a polymer compound (hereinafter also referred to as a polymer as appropriate) and an electron-accepting compound are used. Furthermore, other components may be used as the material for the hole injection layer 3. Hereinafter, the material of these hole injection layers 3 will be described.

(4-4-1-1. Polymer)
The kind of the polymer used as the material for the hole injection layer 3 is arbitrary as long as the effects of the present invention are not significantly impaired. However, among them, a polymer having a hole transporting property (a high molecular weight hole transporting compound (hereinafter, appropriately referred to as “hole transporting polymer”) is preferable, and from this viewpoint, it is 4.5 eV to 5.5 eV. Preferably, the compound has an ionization potential, which is defined by the energy required to emit electrons at the HOMO (highest occupied molecular orbital) level of the material to the vacuum level. In the case of the latter method, for example, when a saturated sweet potato electrode (SCE) is used as a reference electrode, it is obtained by correcting the participation potential measured directly or electrochemically with respect to the reference electrode. It is represented by the following formula ("Molecular Semiconductors", Springer-Verlag, 1985, pp. 98).
Ionization potential = oxidation potential (vs. SCE) + 4.3 eV

  Examples of the hole transporting polymer include aromatic amine compounds, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, and the like. Of these, aromatic amine compounds are preferred from the viewpoints of amorphousness, solubility in solvents, and visible light transmittance.

Of the aromatic amine compounds, aromatic tertiary amine compounds are particularly preferable. In addition, the aromatic tertiary amine compound here is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
The type of the aromatic tertiary amine compound is not particularly limited, but a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less is more preferable from the viewpoint of the surface smoothing effect.

Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (I).

(In the formula (I), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. Ar ^{3 to} Ar ⁵ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, or a divalent aromatic heterocyclic group which may have a substituent. X represents a linking group selected from the following linking group group X1.)

Linking group group X1:

(In the formula, each of Ar ^{11 to} Ar ²⁸ independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group. R ¹ and R ² each independently represents hydrogen. Represents an atom or any substituent.)

In the formula (I), as Ar ^{1 to} Ar ⁵ and Ar ^{11 to} Ar ²⁸ , any monovalent or divalent group derived from any aromatic hydrocarbon ring or aromatic heterocyclic ring is applicable. That is, each of Ar ¹ , Ar ² , Ar ¹⁶ , Ar ^21, and Ar ²⁶ can be a monovalent group. Ar ^{3 to} Ar ⁵ , Ar ^{11 to} Ar ¹⁵ , Ar ^{17 to} Ar ²⁰ , Ar ²² to A divalent group can be applied to each of Ar ²⁵ , Ar ^27, and Ar ²⁸ . These may be the same or different from each other. Moreover, you may have arbitrary substituents.

  Examples of the aromatic hydrocarbon ring include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring. Specific examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.

  Examples of the aromatic heterocycle include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples thereof include 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, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline Ring, cinolin ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

Ar ^{3 to} Ar ⁵ , Ar ^{11 to} Ar ¹⁵ , Ar ^{17 to} Ar ²⁰ , Ar ^{22 to} Ar ²⁵ , Ar ²⁷ , Ar ²⁸ may be one type or two or more types of aromatic hydrocarbon rings exemplified above. And / or two or more divalent groups derived from an aromatic heterocycle may be linked and used.

Furthermore, the group derived from the aromatic hydrocarbon ring and / or aromatic heterocycle of Ar ^{1 to} Ar ⁵ and Ar ^{11 to} Ar ²⁸ may further have a substituent unless it is contrary to the gist of the present invention. Good. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less. The type of the substituent is not particularly limited, and examples thereof include one or more selected from the following substituent group W. In addition, as for a substituent, 1 piece may be substituted independently and 2 or more may be substituted by arbitrary combinations and ratios.

[Substituent group W]
An alkyl group having usually 1 or more, usually 10 or less, preferably 8 or less, such as a methyl group or an ethyl group; an alkenyl group having 2 or more, usually 11 or less, preferably 5 or less carbon atoms, such as a vinyl group. An alkynyl group having usually 2 or more, usually 11 or less, preferably 5 or less, such as an ethynyl group; an alkoxy having a carbon number of usually 1 or more, usually 10 or less, preferably 6 or less, such as a methoxy group or an ethoxy group; A group; an aryloxy group such as a phenoxy group, a naphthoxy group, a pyridyloxy group, etc., usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less; a carbon such as a methoxycarbonyl group or an ethoxycarbonyl group An alkoxycarbonyl group having a number of usually 2 or more, usually 11 or less, preferably 7 or less; a dimethylamino group, a diethylamino group or the like, and usually having 2 or more carbon atoms Usually 20 or less, preferably 12 or less dialkylamino group; diphenylamino group, ditolylamino group, N-carbazolyl group, etc., and usually diarylamino having 10 or more carbon atoms, preferably 12 or more, usually 30 or less, preferably 22 or less Group: an arylalkylamino group having 6 or more carbon atoms, preferably 7 or more, usually 25 or less, preferably 17 or less, such as a phenylmethylamino group; an acetyl group, a benzoyl group or the like, and usually having 2 or more carbon atoms, Usually an acyl group of 10 or less, preferably 7 or less; a halogen atom such as a fluorine atom or a chlorine atom; a haloalkyl group having a carbon number of usually 1 or more, usually 8 or less, preferably 4 or less, such as a trifluoromethyl group; An alkylthio group having 1 to 10 carbon atoms, preferably 6 or less, preferably 6 or less; An arylthio group having usually 4 or more, preferably 5 or more, usually 25 or less, preferably 14 or less, such as a ruthio group, a naphthylthio group, or a pyridylthio group; Or more, preferably 3 or more, usually 33 or less, preferably 26 or less silyl group; trimethylsiloxy group, triphenylsiloxy group, etc., the carbon number is usually 2 or more, preferably 3 or more, usually 33 or less, preferably 26 or less. A siloxy group; a cyano group; an aromatic hydrocarbon ring group having usually 6 or more, usually 30 or less, preferably 18 or less, such as a phenyl group or a naphthyl group; a carbon number such as a thienyl group or a pyridyl group. An aromatic heterocyclic group of 3 or more, preferably 4 or more, usually 28 or less, preferably 17 or less.

Among those described above, Ar ¹ and Ar ² are 1 derived from a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, and a pyridine ring from the viewpoint of the solubility, heat resistance, and hole injection / transport properties of the polymer compound. Is more preferably a phenyl group or a naphthyl group.

Among the above, Ar ^{3 to} Ar ⁵ are divalent benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings from the viewpoint of heat resistance and hole injection / transport properties including redox potential. Group is preferable, and a phenylene group, a biphenylene group, and a naphthylene group are more preferable.

In the formula (I), as R ¹ and R ² , a hydrogen atom or an arbitrary substituent is applicable. These may be the same or different from each other. The type of the substituent is not particularly limited as long as it is not contrary to the gist of the present invention. However, if applicable substituents are exemplified, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silyl group, a siloxy group, an aromatic group A hydrocarbon group and an aromatic heterocyclic group are mentioned. Specific examples thereof include the groups exemplified above in the substituent group W.

Among the above polymers, a polymer containing a repeating unit represented by the following formula (1) is preferable.

  The weight average molecular weight of the hole transporting polymer used as the material of the hole injection layer 3 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, Usually, it is 500,000 or less, preferably 200,000 or less, more preferably 100,000 or less.

  The ratio of the polymer in the hole injection layer 3 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10% by weight or more, preferably 30% by weight in terms of the weight ratio with respect to the whole hole injection layer 3. In addition, it is usually 99.9% by weight or less, preferably 99% by weight or less. In addition, when using 2 or more types of polymers together, it is preferable that these total content is contained in the said range.

(4-4-1-2. Electron-accepting compound)
The kind of the electron-accepting compound used as the material for the hole injection layer 3 is arbitrary as long as the effects of the present invention are not significantly impaired. Examples thereof include onium salts substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pendafluorophenyl) borate and triphenylsulfonium tetrafluoroborate; No. 251067), high-valent inorganic compounds such as ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; aromatic boron compounds such as tris (pentafluorophenyl) borane (JP-A-2003-31365); fullerene derivatives ; Iodine etc. are mentioned. Of the above compounds, an onium salt substituted with an organic group is preferable in terms of having strong oxidizing power, and an inorganic compound having a high valence is preferable, and an onium salt substituted with an organic group in terms of being soluble in various solvents, A cyano compound and an aromatic boron compound are preferable. Furthermore, an onium salt substituted with an organic group is particularly preferable from the viewpoint of achieving both strong oxidizing power and high solubility, and particularly preferably a compound represented by the following formulas (II-1) to (II-3). .

(In the above formulas (II-1) to (II-3), R ¹¹ , R ²¹ and R ³¹ each independently represents an organic group bonded to A ^{1 to} A ³ via a carbon atom. R ¹² , R ²² , R ²³ and R ^{32 to} R ³⁴ each independently represents an arbitrary group, and two or more adjacent groups of R ^{11 to} R ³⁴ may be bonded to each other to form a ring. A ¹ -A ³ are all elements in the long period type periodic table (hereinafter, unless otherwise specified, the term “periodic table” refers to the long period type periodic table). there are, a ¹ represents an element belonging to group 17 of the periodic table, a ² represents an element belonging to group 16 of the periodic table, a ³ is .Z ₁ representing an element belonging to group 15 of the periodic table ^{n1- to} Z ₃ ^n3- each independently represents a counter anion, and n _{1 to} n ₃ each independently represents an ionic value of the counter anion.)

In the above formulas (II-1) to (II-3), R ¹¹ , R ²¹ and R ³¹ each independently represents an organic group bonded to A ^{1 to} A ³ via a carbon atom. Therefore, as R ¹¹ , R ^21, and R ³¹ , the type is not particularly limited as long as it is an organic group having a carbon atom at the bond portion with A ^{1 to} A ³ unless it is contrary to the gist of the present invention.

The molecular weights of R ¹¹ , R ²¹ and R ³¹ are each a value including the substituent, and are usually 1000 or less, preferably 500 or less.
Preferred examples of R ¹¹ , R ²¹ and R ³¹ include alkyl groups, alkenyl groups, alkynyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups from the viewpoint of delocalizing positive charges. Among them, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable because it delocalizes positive charges and is thermally stable.

  The alkyl group includes, for example, a linear, branched or cyclic alkyl group having a carbon number of usually 1 or more and usually 12 or less, preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.

  Examples of the alkenyl group include those having usually 2 or more, usually 12 or less, preferably 6 or less carbon atoms. Specific examples include a vinyl group, an allyl group, and a 1-butenyl group.

  Examples of the alkynyl group include those having usually 2 or more, usually 12 or less, preferably 6 or less. Specific examples include ethynyl group and propargyl group.

  Examples of the aromatic hydrocarbon group include a monovalent group derived from a 5- or 6-membered monocyclic ring or a 2 to 5 condensed ring, and a group in which a positive charge is delocalized on the group. . Specific examples thereof include monovalent groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring, and the like. Can be mentioned.

  Examples of the aromatic heterocyclic group include a monovalent group derived from a 5- or 6-membered monocyclic ring or a 2-4 condensed ring, and a group in which a positive charge is delocalized on the group. . Specific examples thereof include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, triazole 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, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline And monovalent groups derived from a ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.

In the above formulas (II-1) to (II-3), R ¹² , R ²² , R ²³ and R ^{32 to} R ³⁴ each independently represents an arbitrary substituent. Accordingly, the types of R ¹² , R ²² , R ²³ and R ^{32 to} R ³⁴ are not particularly limited as long as they are not contrary to the spirit of the present invention.
The molecular weights of R ¹² , R ²² , R ²³ and R ^{32 to} R ³⁴ are each a value including the substituent, and are usually 1000 or less, preferably 500 or less.

Examples of R ¹² , R ²² , R ²³ and R ^{32 to} R ³⁴ are alkyl groups, alkenyl groups, alkynyl groups, aromatic hydrocarbon groups, aromatic heterocyclic groups, amino groups, alkylamino groups, arylamino groups. , Acylamino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyloxy group, alkylthio group, arylthio group, sulfonyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, cyano Group, hydroxyl group, thiol group, silyl group and the like. Among them, like R ¹¹ , R ^21, and R ³¹ , an organic group having a carbon atom at the bond portion with A ^{1 to} A ³ is preferable from the viewpoint of high electron acceptability. Examples include an alkyl group, an alkenyl group, Alkynyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred. In particular, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable because it has a large electron accepting property and is thermally stable.

Examples of the alkyl group, alkenyl group, alkynyl group, aromatic hydrocarbon group and aromatic heterocyclic group are the same as those described above for R ¹¹ , R ²¹ and R ³¹ .

As described above, the groups exemplified as R ¹¹ , R ²¹ , R ³¹ , R ¹² , R ²² , R ²³ , and R ^{32 to} R ³⁴ are further substituted with other substituents unless they are contrary to the spirit of the present invention. It may be. The type of the substituent is not particularly limited, and examples thereof include a halogen atom in addition to the groups exemplified as R ¹¹ , R ²¹ , R ³¹ , R ¹² , R ²² , R ²³ , and R ^{32 to} R ³⁴ . A cyano group, a thiocyano group, a nitro group, etc. are mentioned. Among these, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferable from the viewpoint of not hindering heat resistance and electron accepting property. In addition, the substituent to be further substituted may be substituted with only one, or two or more may be substituted with any combination and ratio.

In the formulas (II-1) to (II-3), two or more adjacent groups out of R ^{11 to} R ³⁴ may be bonded to each other to form a ring.

In formulas (II-1) to (II-3), A ^{1 to} A ³ are all elements after the third period (third to sixth periods) of the periodic table, and A ¹ is a long period type An element belonging to Group 17 of the periodic table is represented, A ² represents an element belonging to Group 16 and A ³ represents an element belonging to Group 15.

Among these, from the viewpoint of electron acceptability and availability, elements before the fifth period (third to fifth periods) of the periodic table are preferable. That is, A ¹ is preferably any ^one of an iodine atom, a bromine atom, and a chlorine atom, A ² is preferably any one of a tellurium atom, a selenium atom, and a sulfur atom, and A ³ is preferably an antimony atom, an arsenic atom, Any of the phosphorus atoms is preferred.

In particular, from the viewpoint of electron acceptability and compound stability, a compound in which A ¹ in formula (II-1) is a bromine atom or an iodine atom, or A ² in formula (II-2) is a selenium atom or a sulfur atom. The compound which is is preferable, and especially the compound whose A < ¹ > in Formula (II-1) is an iodine atom is especially preferable.

In the formulas (II-1) to (II-3), Z ₁ ^{n1 to} Z ₃ ⁿ³ each independently represents a counter anion. The type of the counter anion is not particularly limited, and may be a monoatomic ion or a complex ion. However, the larger the size of the counter anion, the more the negative charge is delocalized, and the positive charge is also delocalized thereby increasing the electron accepting ability. Therefore, the complex ion is preferable to the monoatomic ion.

In formulas (II-1) to (II-3), n _{1 to} n ₃ are each independently any positive integer corresponding to the ionic valence of counter anions Z ₁ ^{n1 to} Z ₃ ⁿ³⁻ . The values of n _{1 to} n ₃ are not particularly limited, but all are preferably 1 or 2, and particularly preferably 1.

Specific examples of Z ₁ ^{n1- to} Z ₃ ^n3- include hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, sulfate ion, sulfite. Ion, perchlorate ion, perbromate ion, periodate ion, chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypophosphite ion, borate ion , Isocyanate ion, hydrosulfide ion, tetrafluoroborate ion, hexafluorophosphate ion, hexachloroantimonate ion; carboxylate ion such as acetate ion, trifluoroacetate ion, benzoate ion; methanesulfonate ion, trifluoro Sulfonate ions such as romethanesulfonate ion; Alkoxy ions such as methoxy ion and t-butoxy ion For example.

In particular, the counter anions Z ₁ ^{n1 to} Z ₃ ⁿ³ are preferably complex ions represented by the following formulas (II-4) to (II-6) from the viewpoint of the stability of the compound and the solubility in a solvent. In view of the large size, the negative charge is delocalized, and the positive charge is also delocalized to increase the electron accepting ability. Therefore, a complex ion represented by the following formula (II-6) is more preferable.

In formulas (II-4) and (II-6), E ¹ and E ³ each independently represent an element belonging to Group 13 of the long-period periodic table. Of these, a boron atom, an aluminum atom, and a gallium atom are preferable, and a boron atom is preferable from the viewpoint of stability of the compound and ease of synthesis and purification.

In formula (II-5), E ² represents an element belonging to Group 15 of the long-period periodic table. Among these, a phosphorus atom, an arsenic atom and an antimony atom are preferable, and a phosphorus atom is preferable from the viewpoint of stability of the compound, ease of synthesis and purification, and toxicity.

  In the formulas (II-4) and (II-5), X represents a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, and is a fluorine atom from the viewpoint of stability of the compound, ease of synthesis and purification, A chlorine atom is preferable, and a fluorine atom is particularly preferable.

In the formula (II-6), Ar ^{61 to} Ar ⁶⁴ each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group and aromatic heterocyclic group are derived from the same 5- or 6-membered monocyclic ring or 2-4 condensed ring as those exemplified above for R ¹¹ , R ²¹ and R ³¹ . A monovalent group is mentioned. Among these, a monovalent group derived from a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, or an isoquinoline ring is preferable from the viewpoint of stability and heat resistance of the compound.

The aromatic hydrocarbon group and aromatic heterocyclic group exemplified as Ar ^{61 to} Ar ⁶⁴ may be further substituted with another substituent as long as not departing from the gist of the present invention. The type of the substituent is not particularly limited, and any substituent can be applied, but an electron-withdrawing group is preferable.

Examples of preferable electron-withdrawing groups as the substituent that Ar ^{61 to} Ar ⁶⁴ may have include halogen atoms such as fluorine atom, chlorine atom and bromine atom; cyano group; thiocyano group; nitro group; mesyl group Alkylsulfonyl groups such as tosyl group; arylsulfonyl groups such as tosyl group; acyl groups such as formyl group, acetyl group, benzoyl group and the like, usually having 1 or more, usually 12 or less, preferably 6 or less; methoxycarbonyl group, ethoxycarbonyl An alkoxycarbonyl group having 2 or more carbon atoms, usually 10 or less, preferably 7 or less; a phenoxycarbonyl group, a pyridyloxycarbonyl group or the like, and usually having 3 or more carbon atoms, preferably 4 or more and usually 25 or less. An aryloxycarbonyl group having an aromatic hydrocarbon group or an aromatic heterocyclic group of preferably 15 or less; Bonyl group; aminosulfonyl group; trifluoromethyl group, pentafluoroethyl group, etc., a fluorine atom in a linear, branched or cyclic alkyl group having usually 1 or more, usually 10 or less, preferably 6 or less carbon atoms And a haloalkyl group substituted with a halogen atom such as a chlorine atom.

Especially, it is more preferable that at least one group among Ar ^{61 to} Ar ⁶⁴ has one or two or more fluorine atoms or chlorine atoms as substituents. In particular, it is particularly a perfluoroaryl group in which all the hydrogen atoms of Ar ^{61 to} Ar ⁶⁴ are substituted with fluorine atoms from the viewpoint of efficiently delocalizing negative charges and having a suitable sublimation property. preferable. Specific examples of the perfluoroaryl group include a pentafluorophenyl group, a heptafluoro-2-naphthyl group, and a tetrafluoro-4-pyridyl group.
In addition, as for the said substituent, only one may be substituted and two or more may be substituted by arbitrary combinations and ratios.

  The formula amount of the complex ions represented by the formulas (II-4) to (II-6) is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 or more, preferably 300 or more, more preferably 400 or more. Moreover, it is usually 5000 or less, preferably 3000 or less, more preferably 2000 or less. If the formula amount of the complex ion is too small, delocalization of the positive charge and the negative charge is insufficient, so that the electron accepting ability may be decreased, and if the formula amount of the complex ion is too large, The compound itself may interfere with charge transport.

  As a material for the hole injection layer 3, any one of the various electron accepting compounds described above may be used alone, or two or more may be used in any combination and ratio. When two or more kinds of electron accepting compounds are used, two or more kinds of electron accepting compounds corresponding to any one of the formulas (II-1) to (II-3) may be combined. Two or more electron-accepting compounds corresponding to different formulas may be combined.

  The content of the electron-accepting compound in the hole-injecting layer 3 and the composition for the hole-injecting layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is a value with respect to the polymer and the hole-transporting compound described later. The amount is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 100% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. A larger amount of the electron-accepting compound is preferable because it is easier to insolubilize, and the heating time can be insolubilized in a short time. In addition, when using together 2 or more types of electron-accepting compounds, it is made for the total content of these to be contained in the said range.

  In addition, when the hole injection layer 3 is formed or after the formation, the above hole transporting polymer or the following hole transporting compound reacts with the electron accepting compound, so that the hole injection after the formation is performed. In the layer 3, a cation radical and an ionic compound of a hole transporting polymer or a hole transporting compound may be generated.

(4-4-1-3. Low molecular weight hole transporting compound)
As a material for the hole injection layer 3, it is preferable to use a low molecular weight hole transporting compound as necessary.
The low molecular weight hole transporting compound can be appropriately selected from various compounds conventionally used as a hole injecting / transporting thin film forming material in an organic electroluminescence device. Among them, those having high solvent solubility are preferable.

  Preferable examples of the low molecular weight hole transporting compound include aromatic amine compounds. Of these, aromatic tertiary amine compounds are particularly preferred.

  The molecular weight of the low molecular weight hole transporting compound is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 200 or more, preferably 400 or more, more preferably 600 or more, and usually 5000 or less, preferably Is not more than 3000, more preferably not more than 2000, still more preferably not more than 1700, particularly preferably not more than 1400. If the molecular weight is too small, the heat resistance tends to be low, whereas if the molecular weight of the low molecular weight hole transporting compound is too large, synthesis and purification tend to be difficult.

  In addition, a low molecular weight hole transportable compound may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

(4-4-1-4. Other components)
As a material of the hole injection layer 3, other components may be further contained in addition to the above-described polymer, electron accepting compound and hole transporting compound as long as the effects of the present invention are not significantly impaired. Examples of other components include various light emitting materials, electron transporting compounds, binder resins, coatability improving agents, and the like. In addition, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and ratios.

[4-4-2. Formation of hole injection layer]
The formation method of the positive hole injection layer 3 is not specifically limited, It can select suitably according to the above-mentioned material. For example, when the hole injection layer 3 is formed by a wet film formation method, <4-1. It is preferably formed by the procedure described in the method for producing an organic electroluminescent element of the present invention>. That is, it is preferable to use the method for producing an organic electroluminescent element of the present invention when the organic layer to be formed is a hole injection layer.
Hereinafter, a method for forming the hole injection layer 3 by the wet film forming method will be described. However, the procedure up to the formation of the outer edge defining film is the same, so only the portion for forming the hole injection layer 3 which is an organic layer will be described. .

  As the hole injection layer solvent to be contained in the composition for hole injection layer, any solvent can be used as long as the hole injection layer 3 can be formed. However, among the aforementioned polymers, electron-accepting compounds, and low-molecular-weight hole-transporting compounds, those capable of dissolving at least one, particularly two or more, and particularly all three are preferable. Specifically, the solubility of the polymer is usually 0.005% by weight or more, particularly 0.5% by weight or more, particularly 1% by weight or more at room temperature and normal pressure. It is preferable to dissolve 0.001% by weight or more, especially 0.1% by weight or more, particularly 0.2% by weight or more.

  In addition, as the solvent for the hole injection layer, a polymer, an electron-accepting compound, a low-molecular-weight hole-transporting compound, and an inactive substance that can deactivate a free carrier (cation radical) generated from a mixture thereof, or A solvent that does not contain a substance that generates a deactivating substance is preferred.

  The solvent for the hole injection layer is not limited as long as the effects of the present invention are not significantly impaired, and examples thereof include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

  Examples of ether solvents 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-dimethoxybenzene, anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, aromatic ethers such as 2,4-dimethylanisole, and the like.

  Examples of the ester solvent include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. and aromatic esters such as n-butyl.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and the like. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and the like. In addition, dimethyl sulfoxide and the like can also be used. These solvent may use only 1 type and may use 2 or more types by arbitrary combinations and a ratio.

  However, aromatic hydrocarbon solvents such as benzene, toluene, and xylene have a low ability to dissolve the oxidant and the polymer, and are therefore preferably used in a mixture with an ether solvent and an ester solvent.

  The ratio of the hole injection layer solvent to the hole injection layer composition is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50%. It is in the range of not less than weight, usually not more than 99.999% by weight, preferably not more than 99.99% by weight, and more preferably not more than 99.9% by weight. In addition, when mixing and using 2 or more types of solvents as a solvent for positive hole injection layers, it is made for the sum total of these solvents to satisfy | fill this range.

  After the application / film formation of the composition for hole injection layer, the obtained coating film is dried, and the hole injection layer 3 is formed by removing the solvent for hole injection layer. The method of film formation is not limited as long as the effect of the present invention is not significantly impaired as long as patterning is possible. For example, a wet film forming method such as a spray coating method, an ink jet method, a screen printing method, a gravure printing method, a flexographic printing method, a nozzle printing method, an offset printing method, an aerosol method, an aerosol jet method, and the like can be given.

  Among these film forming methods, an ink jet method, a nozzle printing method, and an aerosol jet method are preferable. Since these film forming methods do not use a plate material, the plate material component is dissolved in the solvent for the hole injection layer in the composition for the hole injection layer, and as a result, the plate material component is mixed into the film. There is an advantage that no problem occurs.

  The drying method is, for example, a hot plate method in which a substrate is mounted on a plate (hot plate) and a coating film is heated through the plate, a heater is disposed on the upper surface side and / or the lower surface side of the substrate, and the heater A method of heating the thin film by irradiating electromagnetic waves (for example, infrared rays) from, etc. can be used. One heating means may be used, or two or more heating means may be used in any combination and ratio.

  The thickness of the hole injection layer 3 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

<4-5. Hole transport layer>
The hole transport layer 4 is a layer that transports holes from the hole injection layer 3 side to the light emitting layer 5 side. Examples of the material for forming the hole transport layer 4 include the same compounds as those exemplified as the hole transport compound that may be used by mixing with the hole injection layer 3.

  In addition, for example, polymer materials such as polyarylene ether sulfone containing polyvinyl carbazole, polyvinyl triphenylamine, and tetraphenylbenzidine can be used. In addition, the material of the positive hole transport layer 4 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The hole transport layer 4 is preferably not dissolved in a solvent used for forming other layers (particularly, a layer directly laminated on the hole transport layer 4).
For this reason, a hole transporting compound having a crosslinking group may be used, or an additive having a crosslinking group may be contained and insolubilized by irradiation with active energy rays such as heat and light after the formation of the hole transport layer 4. preferable.

The hole transporting compound having a crosslinking group may be any of a monomer, an oligomer, or a polymer. Examples of the crosslinking group include cyclic ethers such as oxetane and epoxy; unsaturated double bonds such as vinyl group, trifluorovinyl group, styryl group, acrylic group, methacryloyl and cinnamoyl; benzocyclobutane and the like.
The hole transporting compound having a crosslinking group may have only one type of the above-mentioned crosslinking group, or may have two or more types in any combination and ratio.
Examples of hole transporting compounds having a crosslinking group include nitrogen-containing aromatic compound derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives, phthalocyanine derivatives, porphyrin derivatives; Examples include triphenylamine derivatives; silole derivatives; oligothiophene derivatives, condensed polycyclic aromatic derivatives, metal complexes, and the like. Among them, nitrogen-containing aromatic derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives; triphenylamine derivatives, silole derivatives, condensed polycyclic aromatic derivatives, metal complexes, etc. Particularly preferred are triphenylamine derivatives.
Here, the term “derivative” does not exclude a compound to which the term is attached. For example, a “triphenylamine derivative” refers to both triphenylamine and a compound derived from triphenylamine. Shall be included.

The formation method of the positive hole transport layer 4 is not specifically limited, It can select suitably according to the above-mentioned material. For example, when the hole transport layer 4 is formed by a wet film forming method, a composition for a hole transport layer in which the above-described material is dissolved in an appropriate solvent is used <4-1. It is preferably formed by the procedure described in the method for producing an organic electroluminescent element of the present invention>. That is, it is preferable to use the method for producing an organic electroluminescent element of the present invention when the organic layer to be formed is a hole transport layer.
Hereinafter, a method of forming the hole transport layer 4 by a wet film forming method will be described in detail. The details of these methods are described in [4-4-2. This is the same as described in the section “Formation of hole injection layer”. Hereinafter, the part which has a difference especially is demonstrated.

  When the hole transport layer 4 is formed by a wet film formation method, a coating composition is prepared by dissolving the above materials in an appropriate solvent, and the film is formed by using a film formation process and a drying process. To do. These details are described in [4-4-2. This is the same as described in the section “Formation of hole injection layer”. Hereinafter, the wet film forming method will be described in particular.

  As the hole transport layer solvent to be contained in the coating composition for producing the hole transport layer 4, any solvent can be used as long as the hole transport layer 4 can be formed. However, those capable of dissolving the above-described hole transporting compound and polymer material are preferable. It is more preferable to use a solvent that does not dissolve the hole injection layer 3.

  Moreover, as a solvent for hole transport layers, a deactivated substance or a deactivated substance that may deactivate a polymer, an electron accepting compound, a hole transporting compound, and a free carrier (cation radical) generated from a mixture thereof. Solvents that do not contain those that generate are preferred.

  After coating / deposition of the coating composition for producing the hole transport layer 4, the obtained coating film is dried and the hole transport layer solvent is removed, whereby the hole transport layer 4 is formed. The The method of wet film formation is not limited as long as the effects of the present invention are not significantly impaired, and [4-4-2. Any method described in the section “Formation of hole injection layer” can be used.

  The drying method is [4-4-2. There is no other limitation as long as it is the same as the method described in the section “Formation of hole injection layer”.

  The film thickness of the hole transport layer 4 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10 nm or more, preferably 30 nm or more, and usually 300 nm or less, preferably 100 nm or less.

<4-6. Light emitting layer>
The light emitting layer 5 is excited by recombination of holes injected from the anode 2 through the hole injection layer 3 and the like and electrons injected from the cathode 6 between the electrodes to which an electric field is applied. Is the layer.

[4-6-1. (Light emitting layer material)
The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) as a constituent material, and preferably a compound having a hole transporting property (hole transporting compound) or an electron transport. A compound (electron transporting compound) having the following properties: There is no particular limitation on the light-emitting material, and a material that emits light at a desired light emission wavelength and has favorable light emission efficiency may be used. Moreover, it is preferable to contain two or more charge transport compounds. Furthermore, the light emitting layer 5 may contain other components as long as the effects of the present invention are not significantly impaired. In the present invention, it is preferable to use a low molecular weight compound. In addition, a low molecular compound means the compound whose weight average molecular weight is 6000 or less normally, Preferably it is 5000 or less, More preferably, it is 1500 or less.

(4-6-1-1. Light-Emitting Material)
Any known material can be applied as the light emitting material. For example, a fluorescent material or a phosphorescent material may be used, but a phosphorescent material is preferable from the viewpoint of internal quantum efficiency.
For the purpose of improving the solubility in a solvent, it is preferable to reduce the symmetry and rigidity of the molecules of the luminescent material, or to introduce a lipophilic substituent such as an alkyl group.

Hereinafter, although the example of a fluorescent dye is mentioned among light emitting materials, a fluorescent dye is not limited to the following illustrations.
Examples of the fluorescent dye that gives blue light emission (blue fluorescent dye) include perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
Examples of fluorescent dyes that give green light emission (green fluorescent dyes) include quinacridone derivatives and coumarin derivatives.
Examples of fluorescent dyes that give yellow light (yellow fluorescent dyes) include rubrene and perimidone derivatives.
Examples of fluorescent dyes that give red luminescence (red fluorescent dyes) include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzoates. Examples thereof include thioxanthene derivatives and azabenzothioxanthene.

  Next, phosphorescent materials among the light emitting materials will be described. Examples of the phosphorescent material include an organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table.

  Preferred examples of the metal selected from Groups 7 to 11 of the periodic table contained in the phosphorescent organometallic complex include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. . Preferred examples of these organometallic complexes include compounds represented by the following formula (V) or formula (VI).

｛式（Ｖ）中、Ｍは金属を表わし、ｑは上記金属の価数を表わす。また、Ｌ及びＬ’は二座配位子を表わす。ｊは０、１又は２の数を表わす。｝

{In Formula (V), M represents a metal, and q represents the valence of the metal. L and L ′ represent bidentate ligands. j represents a number of 0, 1 or 2. }

｛式（ＶＩ）中、Ｍ⁷は金属を表わし、Ｔは炭素原子又は窒素原子を表わす。Ｒ⁹²〜Ｒ⁹⁵は、それぞれ独立に置換基を表わす。但し、Ｔが窒素原子の場合は、Ｒ⁹⁴及びＲ⁹⁵は無い。｝

{In Formula (VI), M ⁷ represents a metal, and T represents a carbon atom or a nitrogen atom. R ^{92 to} R ⁹⁵ each independently represents a substituent. However, when T is a nitrogen atom, R ⁹⁴ and R ⁹⁵ are absent. }

Hereinafter, the compound represented by the formula (V) will be described first.
In formula (V), M represents an arbitrary metal, and specific examples of preferable ones include the metals described above as metals selected from Groups 7 to 11 of the periodic table.

上記Ｌの部分構造において、環Ａ１”は、置換基を有していてもよい、芳香族炭化水素基又は芳香族複素環基を表わす。 In the formula (V), the bidentate ligand L represents a ligand having the following partial structure.

In the partial structure of L, ring A1 ″ represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.

  Examples of the aromatic hydrocarbon group constituting the ring A1 ″ include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring. Specific examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene. And a monovalent group derived from a ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

  Examples of the aromatic heterocyclic group constituting the ring A1 ″ include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples thereof include a furan ring, a benzofuran ring, a thiophene ring, and a benzoic ring. Thiophene 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 , Benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring , Perimidine ring, key Gelsolin ring, quinazolinone ring, and a monovalent group derived from azulene ring.

In the partial structure of L, ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.
Examples of the nitrogen-containing aromatic heterocyclic group constituting the ring A2 include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples thereof include pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, furopyrrole ring, thienofuran ring, benzoisoxazole Ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, And monovalent group derived from a quinazolinone ring.

Examples of the substituent that each ring A1 ″ or ring A2 may have include: a halogen atom such as a fluorine atom; an alkyl group such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; a methoxycarbonyl group and an ethoxy group Alkoxycarbonyl groups such as carbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dialkylamino groups such as dimethylamino groups and diethylamino groups; diarylamino groups such as diphenylamino groups Carbazolyl group; acyl group such as acetyl group; haloalkyl group such as trifluoromethyl group; cyano group; aromatic hydrocarbon group such as phenyl group, naphthyl group, phenanthyl group and the like.
In addition, as for the said substituent, only 1 may be substituted and 2 or more may be substituted by arbitrary combinations and ratios.

In formula (V), bidentate ligand L ′ represents a ligand having at least one of the following partial structures. In the following formulae, “Ph” represents a phenyl group.

Among these, as L ′, the following ligands are preferable from the viewpoint of the stability of the complex.

  More preferred examples of the compound represented by the formula (V) include compounds represented by at least one of the following formulas (Va), (Vb) and (Vc).

{In Formula (Va), M ⁴ represents the same metal as M, w represents the valence of the metal, and ring A1 ″ represents an aromatic hydrocarbon group which may have a substituent. Ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.}

{In Formula (Vb), M ⁵ represents the same metal as M, w represents the valence of the metal, and ring A1 ″ represents an aromatic hydrocarbon group which may have a substituent or Represents an aromatic heterocyclic group, and ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.}

{In the formula (Vc), M ⁶ represents the same metal as M, w represents the valence of the metal, j represents 0, 1 or 2, ring A1 "and ring A1 'represent Each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and ring A2 and ring A2 ′ are each independently a nitrogen-containing optionally substituted group. Represents an aromatic heterocyclic group.}

  In the above formulas (Va), (Vb) and (Vc), preferred examples of the ring A1 ″ and the ring A1 ′ include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a thienyl group, a furyl group, a benzothienyl group, A benzofuryl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a carbazolyl group, and the like can be given.

  In the above formulas (Va), (Vb) and (Vc), preferred examples of ring A2 and ring A2 ′ include pyridyl group, pyrimidyl group, pyrazyl group, triazyl group, benzothiazole group, benzoxazole group, and benzimidazole group. Quinolyl group, isoquinolyl group, quinoxalyl group, phenanthridyl group and the like.

  Examples of the substituent that the compound represented by any one of the formulas (Va), (Vb), and (Vc) may have include a halogen atom such as a fluorine atom; an alkyl group such as a methyl group and an ethyl group Alkenyl groups such as vinyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; alkoxy groups such as methoxy groups and ethoxy groups; aryloxy groups such as phenoxy groups and benzyloxy groups; dimethylamino groups and diethylamino groups A diarylamino group such as a diphenylamino group; a carbazolyl group; an acyl group such as an acetyl group; a haloalkyl group such as a trifluoromethyl group; a cyano group and the like.

  The carbon number of the substituent is arbitrary as long as the effects of the present invention are not significantly impaired. However, when the substituent is an alkyl group, the carbon number is usually 1 or more and 6 or less. When the substituent is an alkenyl group, the carbon number is usually 2 or more and 6 or less. When the substituent is an alkoxycarbonyl group, the carbon number is usually 2 or more and 6 or less. Moreover, when a substituent is an alkoxy group, the carbon number is 1 or more and 6 or less normally. Moreover, when a substituent is an aryloxy group, the carbon number is 6 or more and 14 or less normally. Moreover, when a substituent is a dialkylamino group, the carbon number is 2 or more and 24 or less normally. Moreover, when a substituent is a diarylamino group, the carbon number is 12 or more and 28 or less normally. When the substituent is an acyl group, the carbon number is usually 1 or more and 14 or less. Moreover, when a substituent is a haloalkyl group, the carbon number is 1 or more and 12 or less normally.

  The above substituents may be linked to each other to form a ring. As a specific example, whether the substituent of the ring A1 ″ and the substituent of the ring A2 are bonded, or the substituent of the ring A1 ′ and the substituent of the ring A2 ′ are bonded, One condensed ring may be formed, and examples of such a condensed ring include a 7,8-benzoquinoline group.

  Among the above-described substituents, the substituents of ring A1 ″, ring A1 ′, ring A2 and ring A2 ′ are more preferably alkyl groups, alkoxy groups, aromatic hydrocarbon groups, cyano groups, halogen atoms, haloalkyl groups. , Diarylamino group and carbazolyl group. In addition, as for the substituents of ring A1 ″, ring A1 ′, ring A2 and ring A2 ′, only one may be substituted or two or more may be in any combination. And may be substituted by a ratio.

Further, the formula (Va), as preferred examples of M ⁴ ~M ⁶ in (Vb) and (Vc) include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold.

  Specific examples of the organometallic complex represented by any one of the above formulas (V), (Va), (Vb) and (Vc) are shown below. However, it is not limited to the following compounds.

  Further, among the organometallic complexes represented by the above formula (V), in particular, as the ligand L and / or L ′, a 2-arylpyridine-based ligand (that is, 2-arylpyridine, an arbitrary substituent group) And a compound having an arbitrary group condensed thereto) are preferable.

  The compounds described in International Publication No. 2005/019373 pamphlet can also be used as the light emitting material.

Next, the compound represented by formula (VI) will be described.
In formula (VI), M ⁷ represents a metal. Specific examples include the metals described above as the metal selected from Groups 7 to 11 of the periodic table. Among these, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold is preferable, and divalent metals such as platinum and palladium are particularly preferable.

In the formula (VI), R ⁹² and R ⁹³ each independently represent 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, It represents at least one selected from the group consisting of an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. Each R ⁹² and R ⁹³ may be the same or different.

Further, in the formula (VI), when T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent a substituent represented by the same examples as R ⁹² and R ⁹³ . Also, if T in formula (VI) is a nitrogen atom, R ⁹⁴ and R ⁹⁵ do not. Each T may be the same or different.

In the formula (VI), R ^{92 to} R ⁹⁵ may further have a substituent. When it has a substituent, there is no restriction | limiting in particular in the kind, Arbitrary groups can be made into a substituent. Moreover, as for the substituent, only 1 may be substituted and 2 or more may be substituted by arbitrary combinations and ratios.
Furthermore, in the formula (VI), any two or more groups of R ^{92 to} R ⁹⁵ may be connected to each other to form a ring.

  Specific examples (T-1 to T-7) of the organometallic complex represented by the formula (VI) are shown below. However, it is not limited to the following examples. In the following chemical formulae, Me represents a methyl group, and Et represents an ethyl group.

  The molecular weight of the compound used as the light emitting material is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 10,000 or less, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and usually 100 or more, Preferably it is 200 or more, More preferably, it is 300 or more, More preferably, it is the range of 400 or more. If the molecular weight is too small, the heat resistance is remarkably reduced, gas generation is caused, the quality of the layer is lowered when the layer is formed, or the morphology of the organic electroluminescent device is changed due to migration or the like. There is a case to do. On the other hand, if the molecular weight is too large, it tends to be difficult to purify the organic compound, or it may take time to dissolve in the solvent.

  In addition, any 1 type may be used for the luminescent material mentioned above, and 2 or more types may be used together by arbitrary combinations and a ratio.

The ratio of the light emitting material in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.05% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more. In addition, it is usually 35% by weight or less, preferably 25% by weight or less, and more preferably 20% by weight or less. If the amount of the light emitting material is too small, uneven light emission may occur. If the amount is too large, the light emission efficiency may be reduced. In addition, when using together 2 or more types of luminescent material, it is made for the total content of these to be contained in the said range.

(4-6-1-2. Hole transporting compound)
Further, the light emitting layer 5 may contain a hole transporting compound as a constituent material. Here, of the hole transporting compounds, examples of the low molecular weight hole transporting compound include the above-mentioned [4-4-1-3. In addition to the various compounds exemplified in the column of “low molecular weight hole transporting compound”, for example, two represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl Aromatic diamines containing the above tertiary amines and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234861), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) Aromatic amine compounds having a starburst structure such as triphenylamine (Journal of Luminescence, 1997, Vol. 72-74, pp. 985), aromatic amine compounds composed of tetramers of triphenylamine (Chemical Communications, 1996, pp. 2175), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9. Spiro compounds such as 9′-spirobifluorene (Synthetic Metals, 1997, Vol. 91, pp. 209), etc. In the light emitting layer 5, only one kind of hole transporting compound is used. Two or more kinds may be used in any combination and ratio.

  The ratio of the hole transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight. In addition, it is usually 65% by weight or less, preferably 50% by weight or less, and more preferably 40% by weight or less. If the amount of the hole transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of hole transportable compounds, it is made for the total content of these to be contained in the said range.

(4-6-1-3. Electron transporting compound)
The light emitting layer 5 may contain an electron transporting compound as a constituent material. Here, among the electron transporting compounds, examples of low molecular weight electron transporting compounds include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND), 2,5, -Bis (6 '-(2', 2 "-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), bathophenanthroline (BPhen), 2,9-dimethyl-4,7 -Diphenyl-1,10-phenanthroline (BCP, bathocuproin), 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD), 4 , 4′-bis (9-carbazole) -biphenyl (CBP), etc. In the light emitting layer 5, only one type of electron transporting compound may be used, or two or more types may be combined arbitrarily. It may be used in combination with not proportion.

  The ratio of the electron transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. In addition, it is usually 65% by weight or less, preferably 50% by weight or less, and more preferably 40% by weight or less. If the amount of the electron transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of electron transport compounds, it is made for the total content of these to be contained in the said range.

[4-6-2. Formation of light emitting layer)
The formation method of the said light emitting layer 5 is not specifically limited, According to the above-mentioned material, it can select suitably, For example, a wet film-forming method and a vacuum evaporation method are mentioned. When the light emitting layer 5 is formed by a wet film forming method, a light emitting layer composition in which the above-described materials are dissolved in an appropriate solvent is used, and <4-1. It is preferably formed by the procedure described in the method for producing an organic electroluminescent element of the present invention>. That is, it is preferable to use the method for producing an organic electroluminescent element of the present invention when the organic layer to be formed is a light emitting layer.
Hereinafter, a method for forming the light emitting layer 5 by the wet film forming method will be described in particular. However, the procedure up to the formation of the outer edge defining film is the same.

  As the light emitting layer solvent to be contained in the coating composition for producing the light emitting layer 5, any solvent can be used as long as the light emitting layer 5 can be formed. However, those capable of dissolving the light-emitting material, the hole transporting compound, and the electron transporting compound described above are preferable. Specifically, the solubility of the light emitting material, the hole transporting compound, or the electron transporting compound is usually 0.01% by weight or more, particularly 0.05% by weight or more, and particularly preferably 0.00% at room temperature and normal pressure. It is preferable to dissolve 1% by weight or more. Suitable examples of the solvent for the light emitting layer are those described in [4-4-2. This is the same as the solvent described in the section “Formation of hole injection layer”.

  The ratio of the solvent for the light emitting layer to the coating composition for producing the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01% by weight or more, preferably 0.1% by weight. Above, more preferably 0.5% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. In addition, when mixing and using 2 or more types of solvents as a solvent for light emitting layers, it is made for the sum total of these solvents to satisfy | fill this range.

  The method of the wet film-forming method for manufacturing the light emitting layer 5 is not limited as long as the effect of the present invention is not significantly impaired. For example, the above [4-4-2. Any method described in the section “Formation of hole injection layer” can be used. The drying method is also described in [4-4-2. The method can be the same as that described in the section “Formation of hole injection layer”, and there is no other limitation.

  The light emitting layer 5 may have a single layer structure, or may have a structure in which a plurality of layers are stacked. In the latter case, the plurality of layers may be layers made of the same material, but may be layers made of different materials.

  The thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. If the thickness of the light emitting layer 5 is too thin, defects may occur in the light emitting layer, and if it is too thick, the driving voltage of the organic electroluminescent element may increase.

<4-7. Cathode>
The cathode 6 serves to inject electrons into the layer on the light emitting layer 5 side. As the material of the cathode 6, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, a metal having a low work function is preferable, for example, tin, magnesium, indium, A suitable metal such as calcium, aluminum, silver, or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy. In addition, the material of the cathode 6 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The film thickness of the cathode 6 is usually the same as that of the anode 2.
Further, for the purpose of protecting the cathode 6 made of a low work function metal, it is preferable to further stack a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased. For this purpose, for example, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used. In addition, these materials may be used only by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

<4-8. Other layers>
The organic electroluminescent element having the layer configuration shown in FIG. 1 has been mainly described above, but the organic electroluminescent element according to the present invention may have another configuration without departing from the gist thereof. For example, an arbitrary layer may be provided between the anode 2 and the cathode 6 in addition to the layers described above, and an arbitrary layer may be omitted.

  For example, as shown in FIG. 2, the organic electroluminescent element 10 b may have a configuration having an electron injection layer 7 and an electron transport layer 8 between the light emitting layer 5 and the cathode 6. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted. For example, as shown in FIG. 3, the organic electroluminescent element 10 c may have a configuration in which the first charge transport layer is the hole injection layer 3 and the second charge transport layer is the electron blocking layer 9. In FIG. 3, the same components as those in FIGS. 1 and 2 are denoted by the same reference numerals, and description thereof is omitted.

  For example, the top and bottom layers of the substrate may be reversed and stacked from the cathode. In this case, for example, as shown in FIG. 4, the organic electroluminescent element 10 d has a configuration including a cathode 6, an electron injection layer 7, an electron transport layer 8, a light emitting layer 5, and an anode 2 on the substrate 1. be able to. 4, the same components as those in FIGS. 1 to 3 are denoted by the same reference numerals, and the description thereof is omitted.

[4-8-1. (Electron transport layer)
The electron transport layer 8 is provided for the purpose of further improving the light emission efficiency of the device, and efficiently transports electrons injected from the cathode 6 between the electrodes to which an electric field is applied in the direction of the light emitting layer 5. Formed from a compound capable of

  The electron transporting compound used for the electron transport layer 8 usually has high electron injection efficiency from the cathode 6 or the electron injection layer 7 described later, and efficiently transports the injected electrons with high electron mobility. A compound that can be used is used. Examples of the compound satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives , Distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds ( JP-A-6-207169), phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide , N-type zinc sulfide, n-type zinc Such as emissions of zinc, and the like. In addition, the material of the electron carrying layer 8 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

There is no restriction | limiting in the formation method of the electron carrying layer 8, For example, the wet film-forming method (Using the composition which melt | dissolved the material for electron carrying layers in the solvent <4-1. Manufacturing method of the organic electroluminescent element of this invention> However, it is particularly preferable to form by the vacuum evaporation method.
Although the film thickness of the electron carrying layer 8 is arbitrary unless the effect of this invention is impaired remarkably, it is 1 nm or more normally, Preferably it is 5 nm or more, and is 300 nm or less normally, Preferably it is the range of 100 nm or less.

[4-8-2. (Electron blocking layer)
The electron blocking layer 9 is generated by preventing electrons moving from the light emitting layer 5 from reaching the hole injection layer 3, thereby increasing the recombination probability of holes and electrons in the light emitting layer 5. Exciton as emission layer 5
There are a role of confining it inside and a role of efficiently transporting holes injected from the hole injection layer 3 in the direction of the light emitting layer 5. In particular, it is effective when a phosphorescent material or a blue light emitting material is used as the light emitting material.

  The characteristics required for the electron blocking layer 9 include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Furthermore, in the present invention, when the light emitting layer 5 is produced by a wet film formation method, the electron blocking layer 9 is preferably compatible with the wet film formation. Examples of the material used for the electron blocking layer 9 include a copolymer of dioctylfluorene and triphenylamine typified by F8-TFB (described in International Publication No. 2004/084260). In addition, the material of the electron blocking layer 9 may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  There is no restriction | limiting in the formation method of the electron blocking layer 9. FIG. For example, it may be formed by a wet film-forming method (procedure described in <4-1. Manufacturing method of organic electroluminescence device of the present invention> using a composition in which a material for an electron blocking layer is dissolved in a solvent) Moreover, you may form by laminating | stacking on the hole injection layer 3 grade | etc., By another method.

[4-8-3. Electron injection layer
The electron injection layer 7 plays a role of efficiently injecting electrons injected from the cathode 6 into the light emitting layer 5. In order to perform electron injection efficiently, the material for forming the electron injection layer 7 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is usually preferably from 0.1 nm to 5 nm.

Furthermore, an organic electron transport compound represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium or rubidium ( (As described in JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.), it is possible to improve the electron injection / transport properties and achieve excellent film quality. preferable. In this case, the film thickness is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.
In addition, the material of the electron injection layer 7 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  There is no restriction | limiting in the formation method of the electron injection layer 7. FIG. For example, it may be formed by a wet film-forming method (procedure described in <4-1. Manufacturing method of organic electroluminescence device of the present invention> using a composition in which a material for an electron injection layer is dissolved in a solvent) Moreover, it can form by laminating | stacking on the light emitting layer 5 with another method.

[4-8-4. Hole blocking layer)
Further, for example, a hole blocking layer may be provided between the light emitting layer 5 and the electron transport layer 8. The hole blocking layer is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 6 side. The hole blocking layer has a role of blocking holes moving from the anode 2 from reaching the cathode 6 and a role of efficiently transporting electrons injected from the cathode 6 toward the light emitting layer 5. Have.

  The physical properties required for the material constituting the hole blocking layer include high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). It is expensive. As a material for the hole blocking layer satisfying such conditions, for example, bis (2-methyl-8-quinolinolato), (phenolato) aluminum, bis (2-methyl-8-quinolinolato), (triphenylsilanolato) Mixed ligand complexes such as aluminum, metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives Styryl compounds such as JP-A-11-242996 and triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole Kaihei 7-41759) and phenanthroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297). It is. Further, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in International Publication No. 2005-022962 is also preferable as a material for the hole blocking layer. In addition, the material of a hole-blocking layer may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

There is no restriction | limiting in the formation method of a hole-blocking layer, For example, it uses the film-forming method (The composition which dissolved the material for hole-blocking layers in the solvent <4-1. Manufacturing method of the organic electroluminescent element of this invention. > May be formed by a vacuum vapor deposition method.
The thickness of the hole blocking layer is arbitrary as long as the effect of the present invention is not significantly impaired, 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.

[4-8-5. Others]
At the interface between the cathode 6 and the light emitting layer 5 or the electron transport layer 8, for example, lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II) (CsCO ₃ ), etc. It is also an effective method to improve the efficiency of the element (Applied Physics Letters, 1997, Vol. 70, pp. 152; 10-74586 gazette; IEEE Transactions on Electron Devices, 1997, Vol.44, pp.1245; SID 04Digest, pp.154 etc.).

  Furthermore, the organic electroluminescent element of the present invention can be configured by laminating components other than the substrate between two substrates, at least one of which is transparent.

In addition, a structure in which a plurality of components (light emitting units) other than the substrate are stacked in a plurality of layers (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interface layer between the steps (between the light emitting units) (when the anode is ITO and the cathode is Al, these two layers), for example, a charge made of vanadium pentoxide (V ₂ O ₅ ) or the like. When a generation layer (Carrier Generation Layer: CGL) is provided, a barrier between steps is reduced, which is more preferable from the viewpoint of light emission efficiency and driving voltage.

  Furthermore, the organic electroluminescent device of the present invention may be configured as a single organic electroluminescent device, or may be applied to a configuration in which a plurality of organic electroluminescent devices are arranged in an array, and an anode and a cathode May be applied to a configuration in which are arranged in an XY matrix.

  In addition, each layer described above may contain components other than those described as materials as long as the effects of the present invention are not significantly impaired.

[5. Image display device]
The image display device of the present invention is characterized in that the organic electroluminescent elements of the present invention are assembled to display an image. Since the organic electroluminescent element is used, there is an advantage that an image display device can be provided in which there is no color unevenness and the boundary between the light emitting region and the non-light emitting region is clear.
In particular, in the method for manufacturing an organic electroluminescent element of the present invention, when the organic layer to be formed is a hole injection layer, a sufficient effect can be obtained even though the outer edge defining film is easily formed. Particularly preferred is an image display device.

  As an image display device including such an organic electroluminescent element, for example, a television, a mobile phone monitor, a mobile terminal monitor, a PC using a passive matrix driven organic electroluminescent display and / or an active matrix driven organic electroluminescent display. Monitor, public information display device, and the like.

[6. Mechanism for obtaining functional membranes without blurring]
According to the method for producing a functional film of the present invention, when the functional film material is applied to a pattern on a substrate, the outer edge defining film forming composition of the present invention is applied to the outside of the pattern boundary. The bleeding at the outer edge of the coating pattern is suppressed, and a stable pattern shape can be obtained. The reason why such an effect is obtained is estimated as follows.

When a solution that does not contain a surfactant is applied, a Marangoni flow is generated due to non-uniform surface tension that occurs on the surface of the film as the liquid film is dried, which induces flow mainly. It is thought that spreading spread occurs from the applied area.
Usually, since the liquid film is dried from the outer edge of the pattern, there is a problem that even if the liquid film is applied accurately inside the pattern, the liquid film spreads outside the pattern.

On the other hand, when a solution containing a surfactant is applied, the surfactant adheres to the substrate at the outer edge of the liquid film, thereby increasing the contact angle of the liquid film to the substrate and suppressing spreading. It is thought.
Since the composition for forming an outer edge defining film of the present invention contains a surfactant, an outer edge defining film having a stable outer edge portion can be formed so as to frame the pattern when applied to the outside of the pattern boundary.

  Furthermore, when a composition for forming a functional film (solution containing no surfactant) is applied to the inside of the pattern, an outer edge defining film containing a surfactant having a stable outer edge is present outside the pattern boundary. The contact angle to the substrate of the composition for forming a functional film at the outer edge of the pattern is increased, the spread of spreading is suppressed, and a functional film having no bleeding (functional film having a stable outer edge of the pattern) can be obtained. It is done.

  In addition, this effect does not greatly depend on the dried state of the outer edge defining film, and any effect can be obtained. On the contrary, it is considered that a higher effect is obtained as the outer edge defining film has a more stable outer edge portion outside the pattern boundary.

Therefore, if such an outer edge regulating film can be formed, the forming method is not limited, but among them, by applying a solution having a surfactant concentration of 0.001% by weight to 0.1% by weight, the outer edge regulating film is formed. It is preferable to form a film.
This is because the coating method is advantageous in terms of cost, and when the concentration is within the above range, the contact angle with respect to the substrate is high, and an outer edge defining film having a stable outer edge portion can be obtained.

  Here, in order to form a functional film without bleeding, it is also conceivable to add a surfactant to the functional film-forming composition. However, it is preferable that the functional film contains as little impurities as possible. The method for producing a functional film of the present invention can be particularly preferably applied when such a high-purity functional film is required.

[7. Advantages of the present invention]
According to the composition for forming an outer edge defining film of the present invention and the method for producing a functional film using the same, spread of spreading (bleeding) at the outer edge of the pattern of the functional film applied on the substrate is suppressed and stable. Pattern shape can be obtained. The present invention is particularly effective when it is preferable that the functional film does not contain a surfactant.

  Further, when the present invention is applied to the formation of the organic layer constituting the organic electroluminescence device, a uniform light emission pattern with less unevenness can be realized without using a complicated and expensive process.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

[Example 1]
(Functional film forming composition)
As a functional film-forming coating solution, a polymer compound having an aromatic amino group represented by the following formula (2) was dissolved in ethyl benzoate so as to have a solid content concentration of 2% by weight. Next, an electron-accepting compound of the following formula (3) is dissolved in the above solution so as to have a solid content concentration of 0.8% by weight, and filtered with a PTFE (Teflon (registered trademark)) filter having a pore size of 0.2 μm. And the resulting solution was used.

(Composition for forming outer edge regulation film)
As a composition for forming an outer edge regulating film of a functional film, a perfluoro group-containing surfactant (S-393 manufactured by AGC Seimi Chemical) was dissolved in ethyl benzoate so as to have a concentration of 0.1% by weight.
When the contact angle of the composition for forming the outer edge regulating film on the washed glass substrate was measured, it was 36.8 °, and the outer edge portion of the liquid droplets was hardly flowed and was stable.

(Boundary formation test)
Next, 0.5 μL (microliter) of the above-mentioned outer edge regulating film forming composition is applied by being discharged from a nozzle having a pore diameter of about 500 μm on the cleaned glass substrate, and then the above functional film forming coating solution is applied. 0.5 μL was applied in the same manner adjacent to the outer edge regulating film, and the state of the boundary between the two coating liquid films at 1 minute after application was confirmed. The distance between the center points of each liquid film was about 2 mm.
As a result of observing the five sets of coating films, the coating films were not mixed in the four groups, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained. On the other hand, the outer edge portion of the functional film that is not in contact with the outer edge defining film flowed and blotted from the time of application using the nozzle.

[Example 2]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 1 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.01% by weight.
The contact angle of the composition for forming the outer edge regulating film with respect to the glass substrate was 45.0 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test with respect to five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 3]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 1 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.005% by weight.
The contact angle of the composition for forming the outer edge defining film with respect to the glass substrate was 36.8 °, and the outer edge portion of the liquid droplets hardly flowed and was stable.
As a result of the boundary formation test on five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 4]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 1 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.001% by weight.
The contact angle of the composition for forming the outer edge regulating film with respect to the glass substrate was 27.0 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test with respect to five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 5]
The surfactant contained in the composition for forming the outer edge regulation film is a surfactant having a polysiloxane structure (BYK (registered trademark) -333 manufactured by Big Chemie Japan), and the concentration is 0.1% by weight, In the same manner as in Example 1, contact angle measurement and boundary formation test were performed.
The contact angle of the composition for forming the outer edge regulating film with respect to the glass substrate was 27.4 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test on five sets of coating films, the three sets did not cause mixing, and in these sets, the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 6]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 5 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.01% by weight.
The contact angle of the composition for forming the outer edge defining film with respect to the glass substrate was 27.7 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test on five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 7]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 5 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.005% by weight.
The contact angle of the composition for forming the outer edge defining film with respect to the glass substrate was 26.2 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test with respect to five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Example 8]
A contact angle measurement and a boundary formation test were performed in the same manner as in Example 5 except that the concentration of the surfactant contained in the outer edge regulating film forming composition was 0.001% by weight.
The contact angle of the composition for forming the outer edge regulating film with respect to the glass substrate was 18.0 °, and the outer edge portion of the droplet did not flow and was stable.
As a result of the boundary formation test with respect to five sets of coating films, no mixing was observed, and the outer edge portion of the functional film in contact with the outer edge defining film was stably maintained.

[Comparative Example 1]
A contact angle measurement and a boundary formation test with a functional film were performed in the same manner as in Example 1 except that ethyl benzoate containing no surfactant was used as the composition for forming an outer edge regulating film.
The contact angle of the outer edge regulating film forming composition with respect to the glass substrate was 4.0 °. Since the contact angle was small, spreading spread occurred and the outer edge portion of the outer edge defining film itself was not stable.
As a result of the boundary formation test for five sets of coating films, mixing occurred in all the sets, and stabilization of the outer edge shape of the functional film was not observed.

[result]
The results of these examples and comparative examples are summarized in the following table.

  The present invention can be widely applied to the field using functional films. Specifically, energy conversion films (photoelectric conversion films, electroluminescent films), charge conduction / insulating films (electrodes, hole transport layers, charge injection) Layer, electrical insulation film, electrical resistance film), optical film (deflection filter film, color filter film, light blocking film (mask)), protective film, smoothing film, adhesive film, etc. It can be widely used in the technical field using the film. In particular, various fields where organic electroluminescent elements are used, such as flat panel displays (for example, for OA computers and wall-mounted televisions) and light sources that make use of characteristics as surface emitters (for example, light sources for copiers, liquid crystal displays) And back light sources for measuring instruments), display panels, marker lamps, and the like.

It is sectional drawing which shows typically an example of the structure of the organic electroluminescent element of this invention. It is sectional drawing which shows typically another example of the structure of the organic electroluminescent element of this invention. It is sectional drawing which shows typically another example of the structure of the organic electroluminescent element of this invention. It is sectional drawing which shows typically another example of the structure of the organic electroluminescent element of this invention. It is a typical top view for explaining a pattern, a pattern outer edge part, a pattern boundary, a pattern boundary outside, and a pattern outside.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Cathode 7 Electron injection layer 8 Electron transport layer 9 Electron blocking layers 10a to 10d Organic electroluminescent device 100 Pattern 101 Pattern outer edge 102 Pattern boundary outer 103 Pattern Outside

Claims (16)

A composition that is formed adjacent to a functional film and forms an outer edge defining film that defines an outer edge of the functional film,
A composition for forming an outer edge regulating film, comprising a surfactant and a solvent. 2. The composition for forming an outer edge regulating film according to claim 1, wherein the contact angle to the glass substrate is 18 ° or more. The composition for forming an outer edge regulating film according to claim 1, wherein the surfactant is contained in an amount of 0.001% by weight to 0.1% by weight. The composition for forming an outer edge regulating film according to any one of claims 1 to 3, wherein the surfactant is a fluorine-based surfactant or a silicone-based surfactant. The composition for forming an outer edge regulating film according to any one of claims 1 to 4, further comprising a material contained in the functional film. The composition for forming an outer edge regulating film according to any one of claims 1 to 5, wherein the functional film is an organic layer of an organic electroluminescence device. The composition for forming an outer edge regulating film according to claim 6, wherein the organic layer is a hole injection layer. Forming an outer edge defining film on the substrate using the outer edge defining film forming composition according to any one of claims 1 to 7, and then forming a functional film adjacent to the outer edge defining film. A method for producing a functional film. After forming an outer edge regulating film on the substrate using the outer edge regulating film forming composition according to any one of claims 1 to 7, an organic layer is formed adjacent to the outer edge regulating film. A method for producing an organic electroluminescent element, characterized by comprising: 10. The method of manufacturing an organic electroluminescent element according to claim 9, wherein the organic layer is formed after the outer edge defining film is formed and before the outer edge defining film is dried. The method for producing an organic electroluminescent element according to claim 9 or 10, wherein the organic layer is a hole injection layer. The method for producing an organic electroluminescent element according to claim 11, wherein the hole injection layer contains a polymer containing a repeating unit represented by the following formula (1).

An organic electroluminescence device comprising an outer edge defining film containing a surfactant and an organic layer formed adjacent to the outer edge defining film on a substrate. The organic electroluminescence according to claim 13, wherein the outer edge defining film is a film formed by using the outer edge defining film forming composition according to any one of claims 1 to 7. element. The organic electroluminescent device according to claim 14, wherein the organic layer is a hole injection layer. An image display device comprising the organic electroluminescent elements according to claim 13 assembled to display an image.

Images