JP2007109524A - Organic el material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide organic EL material obtained by a simple method without providing a barrier rib layer, and having excellent durability and high definition, and its manufacturing method. <P>SOLUTION: The organic EL material has a fine-hole structure between a positive electrode and a negative electrode on a supporting body, and a positive hole transporting layer, a light emitting layer and an electron transporting layer in this order in at least one hole in the fine-hole structure. It is desirable that the organic EL material has any of red light emitting material, green light emitting material and blue light emitting material in at least one hole in the fine-hole structure and the fine-hole structure is a honeycomb porous structure produced by self-organization. The method of manufacturing organic EL material includes a fine-hole structure producing step of producing the fine-hole structure having holes on the surface of the positive electrode on the supporting body and an accommodating step of accommodating the positive hole transporting layer, a light emitting layer and the electron transporting layer which are laminated in this order in each of the holes of the produced fine-hole structure. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic EL material to which a honeycomb-like porous structure produced by self-organization is applied and a method for producing the same.

In recent years, organic EL elements have been actively studied. This is because a hole transport material such as triphenyldiamine (TPD) is deposited on the hole injection electrode by vapor deposition, and a fluorescent material such as aluminum quinolinol complex (Alq ₃ ) is laminated thereon as a light emitting layer, and Mg An element having a basic structure in which a metal electrode (electron injection electrode) having a small work function such as Ag is formed, and an extremely high luminance of several hundred to several tens of thousands cd / m ² can be obtained at a voltage of about 10 V. Has been.

  Such high-brightness and high-efficiency organic EL elements have been obtained so far mainly by thinning low molecular organic materials by vacuum deposition. However, over the past few years, polymer organic EL devices made by thinning polymer organic materials by spin coating have made great strides, making them inexpensive and easy to create, and creating flexible devices. It attracts attention because it is.

  On the other hand, element patterning is indispensable for the production of devices, particularly full-color devices. Several proposals have been made so far for patterning a polymer organic EL element.

For example, Patent Document 1 below proposes a method in which photosensitivity is imparted to a polymer organic EL material and optical patterning is performed. Patent Document 2 and Patent Document 3 below propose a method in which an organic EL material is doped in a photosensitive resin and patterning is performed. In addition, a method using an inkjet has been proposed (see Patent Document 4).
However, in order to use these methods, a partition layer must be provided in advance on the substrate using photolithography or the like, and the development of a simple method has been desired.
In addition, since a complicated process such as a photoresist is performed, a component that is originally not necessary for light emission enters the light emitting layer, and the presence of this component deteriorates durability, resulting in poor definition. .

  On the other hand, in recent years, a technique for producing a film having an ordered structure by utilizing a self-organization phenomenon has been studied. For example, in Non-Patent Document 1 and Non-Patent Document 2, a honeycomb-like porous structure can be produced by self-accumulating droplets condensing from the air and a polymer precipitated at the solvent interface in a three-phase boundary region. It is disclosed. The methods described in these documents use droplets that condense from the air and a polymer that precipitates at the solvent interface, and therefore do not require a complicated manufacturing apparatus.

  However, these documents do not disclose or suggest a specific use of the produced honeycomb porous structure or a specific condition control method according to the use, and the honeycomb porous structure is not organic EL. In order to utilize it as a material, further research and development are necessary.

JP-A-6-13184 Japanese Patent Laid-Open No. 10-69981 Japanese Patent Laid-Open No. 10-289785 JP 2001-76874 A Thin Solid Films, 327-329 (1998), 854-856. Chaos, 9-2 (1999), 308-314

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a high-definition organic EL material which is obtained by a simple method without providing a partition wall layer and has excellent durability and a method for producing the same.

Means for solving the above problems are as follows. That is,
<1> Between the anode and the cathode on the support, having a fine hole structure, and in at least one hole in the fine hole structure, a hole transport layer, a light emitting layer, and an electron transport layer, It is an organic EL material characterized by having it in this order.
<2> The organic EL material according to <1>, wherein the fine pore structure is a honeycomb-like porous structure produced by self-organization.
<3> The method according to any one of <1> to <2>, wherein the at least one hole in the fine hole structure includes any one of a red light emitting material, a green light emitting material, and a blue light emitting material. It is an organic EL material.
<4> The organic EL material according to any one of <1> to <3>, wherein the fine pore structure material is at least one selected from a hydrophobic polymer and an amphiphilic polymer.
<5> The organic EL material according to any one of <1> to <4>, wherein the fine pore structure material contains a black colorant.
<6> The organic EL material according to any one of <1> to <5>, wherein the support is a film having a glass transition temperature (Tg) of 120 ° C. or higher.
<7> The organic EL material according to <6>, wherein the water vapor permeability of the film is 1 × 10 ⁻³ g / m ² · 24 h or more.
<8> A coating liquid containing an organic solvent and a polymer compound is applied to the anode surface on the support, droplets are formed in the resulting film, and the organic solvent and the droplets are evaporated to A microporous structure manufacturing process for manufacturing a microporous structure having a void in the film;
And a containing step of containing a hole transport layer, a light emitting layer, and an electron transport layer so as to be laminated in this order in the pores of the obtained fine pore structure. Is the method.
<9> The method for producing an organic EL material according to <8>, wherein the coating liquid contains a black colorant.

The organic EL material of the present invention has a fine pore structure between an anode and a cathode on a support, and in at least one pore in the fine pore structure, a hole transport layer, a light emitting layer, and An electron transport layer is provided in this order. As a result, a fine pore structure can be formed without going through complicated processes such as photoresist, so that unnecessary components are not required for light emission, and it is possible to provide a high-definition organic EL material having excellent durability. . The organic EL material preferably has a honeycomb-like porous structure in which a fine pore structure is produced by self-organization.
Further, the mechanism by which the honeycomb porous structure is formed is estimated as follows. When the hydrophobic organic solvent evaporates, water condenses on the surface of the solvent whose temperature is lowered due to the removal of latent heat, and becomes fine droplets and adheres to the polymer solution surface. The action of the hydrophilic portion in the polymer solution reduces the surface tension between water and the hydrophobic organic solvent and prevents water droplets from aggregating and coalescing into one mass. The droplets are transferred and collected by the solvent flow based on solvent evaporation and filling from the surroundings, and are further closely packed by the transverse capillary force. Finally, the water evaporates and the polymer remains in a regular and honeycomb form.

In the method for producing an organic EL material of the present invention, a coating liquid containing an organic solvent and a polymer compound is applied to the anode surface on a support, droplets are formed in the obtained film, and the organic solvent and A microporous structure manufacturing step of evaporating the liquid droplets to create a microporous structure having holes in the film;
And a housing step of housing the hole transport layer, the light emitting layer, and the electron transport layer so as to be stacked in this order in the pores of the obtained micro-hole structure. As a result, an organic EL material can be manufactured by a simple method without providing a partition layer using photolithography or the like.

  According to the present invention, a conventional problem can be solved, and a high-definition organic EL material that is obtained by a simple method without providing a partition layer and has excellent durability and a method for manufacturing the same can be provided. Can do.

(Organic EL material)
The organic EL material of the present invention has a fine pore structure between an anode and a cathode on a support, and in at least one pore in the fine pore structure, a hole transport layer, a light emitting layer, and It has an electron transport layer in this order, and further has other configurations as necessary.
The fine pore structure is preferably a honeycomb-like porous structure produced by self-organization.
In the case of obtaining a full color device, the organic EL material has any one of a red light emitting material, a green light emitting material, and a blue light emitting material in at least one hole in the fine hole structure.
The fine hole structure may have the hole transport layer, the light emitting layer, and the electron transport layer in this order in at least one hole, but in as many holes as possible. It is preferable to have these, and it is most preferable to have these in all the holes. Further, when the fine pore structure includes any one of a red light emitting material, a green light emitting material, and a blue light emitting material, it includes any of a red light emitting material, a green light emitting material, and a blue light emitting material. However, it is preferable that any of the light emitting materials of the respective colors is included.

-Support-
The support is not particularly limited as long as it has a certain degree of strength, and can be appropriately selected according to the purpose. Examples thereof include films, glasses, metals, and silicon wafers. Among these, From the viewpoint of weight reduction and brittleness, a film is preferable.
The film is not particularly limited as long as the laminate can be held on the film when it is formed into a film. For example, a thermoplastic film having gas barrier properties is preferable.
Examples of the thermoplastic film having gas barrier properties include methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide resin. , Cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethylene naphthalate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin And those made of thermoplastic resins such as alicyclic modified polycarbonate resins and acryloyl compounds.
Moreover, the polymer of General formula (1) can also be used in US Patent 2005-0112378.

The glass transition temperature (Tg) of the film is preferably 120 ° C. or higher, and more preferably 120 to 400 ° C. When the Tg is less than 120 ° C., the substrate may be deformed by heat generated during the production of indium tin oxide (ITO) or a thin film transistor (TFT).
The Tg can be measured by, for example, a differential thermal balance (manufactured by Rigaku).
The water vapor permeability of the film is preferably 1 × 10 ⁻³ g / m ² · 24 h or more from the viewpoint of storage stability of the element (organic EL material), and 1 × 10 ⁻³ to 1 × 10 ^−6. It is more preferable that it is g / m < ² > * 24h. When the water vapor permeability is larger than 1 × 10 ⁻³ g / m ² · 24 h, the device may be deteriorated by passing water molecules.
Here, the water vapor permeability can be measured by, for example, the MOCON method.

--- Gas barrier layer--
In the case where a film is used in the support, it is preferable that the gas barrier layer is disposed on at least one side of the film.
The material of the gas barrier layer is not particularly limited as long as a gas barrier can be performed. For example, an oxide containing at least one selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, and the like, Examples thereof include inorganic substances such as nitrides and oxynitrides.

In particular, as the gas barrier layer, it is more preferable to use a metal compound thin film made of silicon oxide or silicon oxynitride in order to achieve both water vapor barrier properties and high transparency.
The silicon oxide is denoted as SiO _x, for example, in the case of using SiO _x as inorganic layer, in order to achieve both a good water vapor barrier properties and high light transmittance, and 1.6 <x <1.9 It is desirable to do. Silicon oxynitride is expressed as SiO _x N _y , and the ratio of x and y is an oxygen-rich film when importance is attached to improving adhesion, and 1 <x <2, 0 <y < 1 is preferable, and when importance is placed on improving the water vapor barrier property, a nitrogen-rich film is preferable, and 0 <x <0.8 and 0.8 <y <1.3 are preferable.

The method for forming the gas barrier layer is not particularly limited as long as a desired thin film can be formed. For example, a sputtering method, a vacuum evaporation method, an ion plating method, a plasma CVD method, and the like are preferable.
More specifically, it is preferable to form the film by the methods described in Japanese Patent No. 3430344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774.

The thickness of the gas barrier layer is not particularly limited, but if it is too thick, there is a risk of cracking due to bending stress, and if it is too thin, the film is distributed in an island shape.
From such a viewpoint, the thickness of the gas barrier layer is preferably 5 to 1,000 nm, more preferably 10 to 1,000 nm, and particularly preferably 10 to 200 nm.

  When two or more gas barrier layers are formed, each layer may be a layer having the same composition or a layer having a different composition.

-Organic layer-
The support preferably has an organic layer adjacent to the gas barrier layer in order to improve the brittleness and barrier properties of the gas barrier layer.
As the organic layer, for example, as described in US 2005-0112378, (1) a method using an inorganic oxide layer produced using a sol-gel method, and (2) after laminating an organic material by coating or vapor deposition It can be formed using a method of curing with ultraviolet rays or electron beams. Moreover, you may use combining the method of said (1) and (2), for example, after forming a 1st organic layer by the method of said (1) on a resin film, producing a gas barrier layer, Further, a second organic layer may be formed thereon by the method (2).

There is no restriction | limiting in particular about the shape of the said support body, a structure, a magnitude | size, etc., It can select suitably according to a use, the objective, etc.
In general, the support is preferably plate-shaped.
The structure of the support may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members. .

  The support may be colorless and transparent, or may be colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the light emitting material.

  When a thermoplastic material is used as the support, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

-Anode-
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the application and purpose. The electrode material can be selected as appropriate. In addition, it is preferable that the said anode is normally provided as a transparent anode.

Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.
More specifically, conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metals such as gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organics such as polyaniline, polythiophene and polypyrrole Examples thereof include conductive materials and laminates of these and ITO. Among these, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like.

  Examples of the anode include a printing method, a wet method such as a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD method and a plasma CVD method. Can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material constituting the material. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like, and vacuum deposition or sputtering is performed by overlaying a mask. It may be performed by a lift-off method or a printing method.

  There is no restriction | limiting in particular as a formation position of the said anode, Although it can select suitably according to a use and the objective, It is preferable to form on the said support body. In this case, the anode may be formed on the entire one surface of the support or may be formed on a part thereof.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is preferably about 10 nm to 50 μm, and more preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / or less, and more preferably 10 ² Ω / or less. When the anode is transparent, it may be colorless and transparent or colored and transparent.
In order to extract emitted light from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is described in detail in the book “New Development of Transparent Electrode Film” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

-Cathode-
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the application and purpose. It can select suitably from electrode materials.

Examples of the material for the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof.
More specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys. , Magnesium-silver alloys, rare earth metals such as indium and ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among the above-described examples, the cathode material is preferably an alkali metal or an alkaline earth metal from the viewpoint of electron injection, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Say.

  The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of the said cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the material of the cathode, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  The patterning for forming the cathode may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like, and is performed by vacuum deposition or sputtering with a mask overlapped. Alternatively, it may be performed by a lift-off method or a printing method.

There is no restriction | limiting in particular as a formation position of the said cathode, You may form in the whole on an organic compound layer, and you may form in the part.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride, oxide or the like may be inserted between the cathode and the fine pore structure with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.
The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode, and cannot be generally defined, but is preferably about 10 nm to 5 μm, more preferably 50 nm to 1 μm.
The cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

-Hole transport layer-
The hole transport layer is a layer having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
Examples of the material constituting the hole transport layer include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon, etc. Is mentioned.

There is no restriction | limiting in particular as a formation method of the said positive hole transport layer, It can form suitably by any of dry-type film forming methods, such as a vapor deposition method and a sputtering method, the transfer method, and the printing method.
The thickness of the hole transport layer is preferably 500 nm or less, more preferably 1 to 500 nm, still more preferably 5 to 200 nm, and more preferably 10 to 100 nm, from the viewpoint of lowering the driving voltage. It is particularly preferred.

The hole transport layer may have a hole injection layer on the surface on the anode side or on the surface opposite to the anode. The hole injection layer is preferably provided on the surface on the anode side of the hole transport layer.
As the material and the formation method of the hole injection layer, the same materials as those in the hole transport layer described above are preferably exemplified.
The thickness of the hole injection layer is preferably 500 nm or less, more preferably 0.1 to 200 nm, still more preferably 0.5 to 100 nm, from the viewpoint of lowering the driving voltage. It is especially preferable that it is 1-100 nm.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

-Light emitting layer-
The light-emitting layer has a function of receiving holes from an anode and a hole transport material, receiving electrons from a cathode and an electron transport material, and providing a field for recombination of holes and electrons to emit light when an electric field is applied. It is.

There is no restriction | limiting in particular as a material which comprises the said light emitting layer, A fluorescent luminescent material may be sufficient and a phosphorescent luminescent material may be sufficient.
Examples of the fluorescent light-emitting material include rhodamine or derivatives thereof, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarins or the like. Derivatives, condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, distyrylbiphenyl derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives , Cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quino Various metal complexes represented by metal complexes of the metal complex and pyrromethene derivatives Nord derivatives, polythiophene, polyphenylene, polymeric compounds such as polyphenylene vinylene, compounds such as organic silane derivatives, and the like.

In the fluorescent light emitting material, as a red color forming material suitable for obtaining a full color device, among the above exemplary compounds, from the viewpoint of being able to form a uniform and stable light emitting layer that is low molecular and soluble in an aqueous solution. Rhodamine or a derivative thereof may be mentioned.
Examples of the rhodamine or derivatives thereof include rhodamine B, rhodamine B base, rhodamine 6G, rhodamine 101 perchlorate and the like. These may be used alone or in combination of two or more.
Preferred examples of the green light emitting material include quinacridone derivatives from the same viewpoint as the red light emitting material.
Preferred examples of the blue light-emitting material include a tetraphenylbutadiene derivative, coumarin or a derivative thereof, and a distilbiphenyl derivative from the viewpoint of low molecular weight and solubility in an aqueous solution or a mixed solution of water and alcohol.
Examples of the coumarin or derivatives thereof include coumarin, coumarin-1, coumarin-6, coumarin-7, coumarin 120, coumarin 138, coumarin 152, coumarin 153, coumarin 311, coumarin 314, coumarin 334, coumarin 337, coumarin 343. Etc. These may be used alone or in combination of two or more.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
Although there is no restriction | limiting in particular as said transition metal atom, For example, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, platinum etc. are mentioned suitably, Among these, rhenium, iridium, and platinum are preferable.
Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Yamamoto. The ligand described in Akio's book "Organometallic Chemistry-Fundamentals and Applications-", published in 1982 by Hankabosha, etc. can be mentioned.
More specifically, halogen ligands (for example, chlorine ligands), nitrogen-containing heterocyclic ligands (for example, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketone ligands (for example, acetylacetone) Etc.), carboxylic acid ligands (for example, acetic acid ligands, etc.), carbon monoxide ligands, isonitrile ligands, cyano ligands are preferred, and among these, nitrogen-containing heterocyclic coordination A child is preferred.
The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Further, different metal atoms may be contained simultaneously.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass.

  There is no restriction | limiting in particular as a formation method of the said light emitting layer, It can form suitably by any of dry film forming methods, such as a vapor deposition method and a sputtering method, the transfer method, and the printing method.

The light emitting layer may be composed of only the above-described light emitting material, or may be a mixed layer of a host material and a light emitting material. Moreover, the said light emitting layer may be 1 layer, or may be 2 or more layers, and each layer may light-emit with a different luminescent color, and a dopant may be used individually by 1 type, 2 types. You may use the above together. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
On the other hand, each color light emitting material described above may be included in the holes included in the fine hole structure in a mosaic shape, or may be included in stripes by dividing the color to be emitted for each predetermined region, A section of each colorant may be determined in a predetermined area, and this may be repeated regularly.

The host material is preferably a charge transport material.
More specifically, for example, those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, those having an arylsilane skeleton, Examples thereof include materials exemplified in the section of transport materials and electron transport materials described later. These may be used singly or in combination of two or more. When two or more are used in combination, for example, an electron transporting host material and a hole transporting host material The structure which mixed these is mentioned.

  Although there is no restriction | limiting in particular in the thickness of the said light emitting layer, Usually, it is preferable that it is 1-500 nm, It is more preferable that it is 5-200 nm, It is especially preferable that it is 10-100 nm.

-Electron transport layer-
The electron transport layer is a layer having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
Examples of the material constituting the electron transport layer include triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides. Derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Examples thereof include various metal complexes typified by metal complexes, organosilane derivatives, and the like.

There is no restriction | limiting in particular as a formation method of the said electron carrying layer, It can form suitably by any of dry film forming methods, such as a vapor deposition method and a sputtering method, the transfer method, and the printing method.
The thickness of the electron transport layer is preferably 500 nm or less, more preferably 1 to 500 nm, still more preferably 5 to 200 nm, and further preferably 10 to 100 nm from the viewpoint of lowering the driving voltage. It is particularly preferred.

The electron transport layer may have an electron injection layer on the surface on the cathode side or the surface opposite to the cathode side. The electron injection layer is preferably provided on the cathode side surface of the electron transport layer.
About the material of the said electron injection layer, and the formation method, the thing same as the thing in the electron carrying layer mentioned above is mentioned suitably.
In addition, the thickness of the electron injection layer is preferably 500 nm or less, more preferably 0.1 to 200 nm, further preferably 0.2 to 100 nm, and 0.5 to 50 nm. Is particularly preferred.
The electron injection layer and the electron transport layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
In the present invention, a hole blocking layer may be provided as the organic compound layer adjacent to the light emitting layer on the cathode side.
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, and phenanthroline derivatives such as BCP.
The thickness of the hole blocking layer is preferably 1 to 500 nm, more preferably 5 to 200 nm, and particularly preferably 10 to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Protective layer-
The entire organic EL material of the present invention may be protected by a protective layer.
The material contained in the protective layer is not particularly limited as long as it has a function of suppressing the entry of elements that promote element deterioration such as moisture and oxygen into the element.
More specifically, metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, Fe ₂ O ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerizing a fluorine-containing copolymer having a cyclic structure in the copolymer main chain. Coalescence, 1% by weight of the water absorbing material water absorption, moisture-proof substance 0.1% or less water absorption, and the like.

  There is no restriction | limiting in particular about the formation method of the said protective layer, For example, a vacuum evaporation method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method ( High frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

-Sealing-
Furthermore, the entire organic EL material of the present invention may be sealed using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the organic EL material.
The moisture absorbent is not particularly limited, and examples thereof include barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride, and fluorine. Examples thereof include cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide.
The inert liquid is not particularly limited, and examples thereof include paraffins, liquid paraffins, fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorinated solvents, and silicone oils.

The organic EL material of the present invention emits light by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Can do.
Regarding the driving method of the organic EL material of the present invention, each of JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in the publications, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, and the like can be applied.

-Fine pore structure-
The fine pore structure material in the fine pore structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from a hydrophobic polymer and an amphiphilic polymer is suitable. is there.
The fine pore structure preferably contains a black colorant in the fine pore structure material from the viewpoint of functioning as a black matrix.

-Polymer-
--Hydrophobic polymer--
There is no restriction | limiting in particular as said hydrophobic polymer, According to the objective, it can select suitably according to the objective, For example, vinyl polymer (For example, polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide) , Polymethacrylamide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyhexafluoropropene, polyvinyl ether, polyvinyl carbazole, polyvinyl acetate, polyvinyl carbazole, polytetrafluoroethylene, etc., polyester (eg, polyethylene terephthalate, polyethylene) Naphthalate, polyethylene succinate, polybutylene succinate, polylactic acid, etc.), polylactone (eg polycaprolactone, etc.), polyamide or poly Imides (eg, nylon or polyamide acid), polyurethanes, polyureas, polycarbonates, polyaromatics, polysulfones, polyethersulfones, polysiloxane derivatives, and the like. From the viewpoints of solubility, optical physical properties, electrical physical properties, film strength, elasticity, and the like, these may be homopolymers as necessary, or may take the form of copolymers or polymer blends. In addition, you may use these polymers as a mixture of 2 or more types of polymers as needed.

-Amphiphilic polymer-
The amphiphilic polymer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polyacrylamide is a main chain skeleton, a dodecyl group is a hydrophobic side chain, and a carboxyl group is a hydrophilic side chain. Examples thereof include an amphiphilic polymer and a polyethylene glycol / polypropylene glycol block copolymer.
The hydrophobic side chain is a non-polar linear group such as an alkylene group or a phenylene group, and has a hydrophilic group such as a polar group or an ionic dissociation group up to the terminal except for a linking group such as an ester group or an amide group. It is preferable that the structure does not branch. As the hydrophobic side chain, for example, when an alkylene group is used, it is preferably composed of 5 or more methylene units.
The hydrophilic side chain preferably has a structure having a polar part, an ionic dissociation group, or a hydrophilic part such as an oxyethylene group at the end via a linking part such as an alkylene group.

  The ratio between the hydrophobic side chain and the hydrophilic side chain differs depending on the size, nonpolarity, polarity strength, hydrophobic strength of the hydrophobic organic solvent, etc. The ratio (hydrophobic side chain / hydrophilic side chain) is preferably 3/1 to 1/3. In the case of a copolymer, a block copolymer in which a hydrophobic side chain and a hydrophilic side chain form a block as long as it does not affect the solubility in a hydrophobic solvent, rather than an alternating polymer of hydrophilic side chains of hydrophobic side chains. It is preferable that

  The number average molecular weight (Mn) of the hydrophobic polymer and the amphiphilic polymer is preferably 1,000 to 10,000,000, and more preferably 5,000 to 1,000,000.

Although the honeycomb structure film can be formed with only the hydrophobic polymer, it is preferably used together with the amphiphilic polymer.
The composition ratio (mass ratio) between the hydrophobic polymer and the amphiphilic polymer is preferably 99: 1 to 50:50, and more preferably 90:10 to 80:20. When the ratio of the amphiphilic polymer is less than 1% by mass, a uniform honeycomb structure may not be obtained. On the other hand, when the ratio of the amphiphilic polymer exceeds 50% by mass, the stability of the film, particularly the mechanical stability may not be sufficiently obtained.

  The hydrophobic polymer and the amphiphilic polymer are also preferably polymerizable (crosslinkable) polymers having a polymerizable group in the molecule. In addition, a polymerizable polyfunctional monomer is blended together with the hydrophobic polymer or the amphiphilic polymer, and a honeycomb film is formed by this blend. Then, a thermosetting method, an ultraviolet curing method, an electron beam curing method, and the like are known. It is also preferable to perform a curing treatment by the method.

The polyfunctional monomer used in combination with the hydrophobic polymer or the amphiphilic polymer is preferably a polyfunctional (meth) acrylate from the viewpoint of reactivity. Examples of the polyfunctional (meth) acrylate include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol caprolactone adduct hexaacrylate or a modified product thereof, epoxy acrylate oligomer, polyester acrylate oligomer, Urethane acrylate oligomer, N-vinyl-2-pyrrolidone, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or a modified product thereof can be used. These polyfunctional monomers are used singly or in combination of two or more from the balance of scratch resistance and flexibility.
When the hydrophobic polymer and the amphiphilic polymer are a polymerizable (crosslinkable) polymer having a polymerizable group in the molecule, they react with the polymerizable group of the hydrophobic polymer and the amphiphilic polymer. It is also preferable to use a polymerizable polyfunctional monomer in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can be cured by a polymerization reaction to form an antireflection film.

Examples of the radical photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, Examples include disulfide compounds, fluoroamine compounds, and aromatic sulfoniums.
Examples of the acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
Examples of the benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.
Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples of the radical photopolymerization initiator are also described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, Inc., published in 1991).
Further, as a commercially available photocleavable photoradical polymerization initiator, Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals Co., Ltd. and the like are preferable examples.
It is preferable to use the said photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, and it is more preferable to use it in the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the external photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, and thioxanthone.

As said thermal radical initiator, an organic peroxide, an inorganic peroxide, an organic azo compound, an organic diazo compound, etc. can be used, for example.
Specific examples of the organic peroxide include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, and butyl hydroperoxide. Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), and the like. Examples of the diazo compound include diazoaminobenzene, p-nitrobenzenediazonium, and the like.

  The polymer concentration of both the hydrophobic polymer and the amphiphilic polymer to be dissolved is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass. If the polymer concentration is less than 0.01% by mass, the obtained film may have insufficient mechanical strength, or the pore size and arrangement may be disturbed. If it exceeds, it may be difficult to obtain a sufficient honeycomb structure.

-Black colorant-
There is no restriction | limiting in particular as said black coloring agent, Although it can select suitably according to the objective, For example, a black pigment, a black dye, etc. are mentioned suitably.
Examples of the black pigment include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the black dye include C.I. I. Reactive Black 3, C.I. I. Reactive Black 4, C.I. I. Reactive Black 7, C.I. I. Reactive Black 11, C.I. I. Reactive Black 12, C.I. I. Reactive Black 17; C.I. I. Basic Black 2, C.I. I. B. Basic Black 8; I. Direct Black 19, C.I. I. Direct black 22, C.I. I. Direct black 32, C.I. I. Direct Black 38, C.I. I. Direct black 51, C.I. I. Direct Black 56, C.I. I. Direct Black 71, C.I. I. Direct Black 74, C.I. I. Direct Black 75, C.I. I. Direct Black 77, C.I. I. Direct black 154, C.I. I. Direct black 168, C.I. I. Direct black 171; I. Food Black 1, C.I. I. Food black 2 etc. are mentioned.
Among these black colorants, carbon black is particularly preferable from the viewpoints of availability and durability.

  The content of the black colorant in the fine pore structure is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 0.01 to 50% by mass with respect to the fine pore structure material, and 0 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If the content is less than 0.01% by mass, the concentration may be insufficient and the contrast may be lowered. If the content exceeds 50% by mass, the contrast performance may be saturated and the film quality may be deteriorated.

  The honeycomb structure in the honeycomb-shaped porous film produced by the self-organization means a structure in which pores having a fixed shape and a fixed size are continuously and regularly arranged. This regular arrangement is two-dimensional in the case of a single layer and regular in three dimensions in the case of a multilayer. This regularity is arranged so that a plurality of (for example, six) holes surround one hole in a two-dimensional manner, and three-dimensionally like a face-centered cubic or hexagonal crystal structure. However, depending on the manufacturing conditions, other regularity may be exhibited.

  In producing the honeycomb structure, since it is essential to form fine water droplet particles on the polymer solution, the solvent to be used is preferably water-insoluble. Examples of the water-insoluble solvent include halogen-based organic solvents such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; water-insoluble such as methyl isobutyl ketone Ketones; ethers such as diethyl ether; carbon disulfide; and the like. These may be used singly or as a mixed solvent in which these solvents are combined.

The pore diameter in the fine pore structure is preferably 100 μm or less, more preferably 1 μm or more and 50 μm or less, and particularly preferably 1 μm or more and 20 μm or less. When the diameter of the pores exceeds 100 μm, each strength is lowered, and it may be easily broken during the stretching process.
Here, in order to reduce the pore diameter of the fine pore structure, it is effective to promote rapid drying. For example, it is effective to use a low-boiling point solvent as the solvent used, raise the support temperature, or increase the developing speed to reduce the initial developing liquid thickness.

  Although the thickness of the fine pore structure is approximately the pore size size to 200 μm, it is possible to provide a thick layer without pores on the support side by increasing the concentration of the developed polymer. In this case, the thickness of the thick layer without voids can be controlled within a range of 0 to 500 μm.

  Here, FIG. 1 shows a schematic diagram of an example of the organic EL material of the present invention, and a black honeycomb porous structure 4 is formed between an anode 2 and a cathode 3 provided on a support 1, The hole transport layer 6, the light emitting layer 7, and the electron transport layer 8 are laminated in this order in the pores 5, 5... Of the honeycomb-like porous structure.

-Application-
The organic EL material of the present invention does not require an unnecessary component for light emission, has excellent durability, and has high definition. For example, a computer, an on-vehicle display, an outdoor display, a household device, a commercial use It can be suitably used in various fields including equipment, home appliances, traffic-related indicators, clock indicators, calendar indicators, luminescent screens, audio equipment, and the like.

(Method for producing organic EL material)
The method for producing an organic EL material according to the present invention includes a fine pore structure manufacturing step, a housing step, and further includes other steps as necessary.

-Microporous structure fabrication process-
The fine pore structure preparation step includes an organic solvent and a polymer compound, preferably a liquid containing a black colorant is cast on the anode surface on the support to form a film, and droplets are formed in the film. Forming a film having pores in the film by evaporating the organic solvent and the droplets. The method for forming the anode on the support is as described in the section of the anode.

  There is no restriction | limiting in particular as said casting method, According to the objective, it can select suitably, For example, a slide method, an extrusion method, a bar method, a gravure method etc. are mentioned.

  As an environment in which the film is formed, it is preferable that the relative humidity is in the range of 50 to 95%. If the relative humidity is less than 50%, water condensation on the solvent surface may be insufficient, and if it exceeds 95%, it may be difficult to control the environment and maintain uniform film formation. is there.

Further, as the environment for forming the film, it is preferable to apply a steady air with a constant air flow in addition to the relative humidity. The relative wind speed with respect to the film is preferably 0.1 to 20 m / s. If the wind speed is less than 0.1 m / s, it may be difficult to control the environment, and if it exceeds 20 m / s, the solvent surface may be disturbed and a uniform film may be difficult to obtain.
In addition, the direction in which the steady wind is applied can be produced in any direction of 0 to 90 ° with respect to the support surface, but 0 to 60 ° is preferable in order to improve the uniformity of the honeycomb structure.

  As the gas whose humidity and flow rate are controlled during the film formation, for example, an inert gas such as nitrogen gas or argon gas can be used in addition to air, but dust removal treatment such as passing through a filter in advance is possible. It is preferable to apply. Since dust in the atmosphere acts as a condensation nucleus of water vapor and affects film formation, it is preferable to install a dust removal facility or the like at the manufacturing site.

  The environment in which the film is formed is preferably strictly controlled by using a commercially available constant dew point humidity generator or the like. The air volume is preferably controlled with a blower or the like, and it is preferable to use a closed space in order to prevent the influence of outside air. In addition, it is preferable to set a gas introduction / extraction path and a film formation environment so that the gas is replaced by a laminar flow. Furthermore, it is preferable to monitor the temperature, humidity, flow rate and the like with a measuring instrument in order to control the film formation quality. In order to control the hole diameter and film thickness with high accuracy, it is essential to strictly manage these parameters (especially humidity and flow rate).

Here, in the fine hole structure, when holes do not penetrate, hole transport from the anode to the hole transport layer cannot be performed, and therefore it is necessary to penetrate the holes.
In this case, examples of a method of penetrating the holes include a method of removing a film remaining between the hole bottom and the anode by irradiating a laser beam.

-Containment process-
In the accommodation step, the hole transport layer, the light emitting layer, and the electron transport layer are accommodated in this order in the pores of the fine pore structure, and other materials are accommodated as necessary. It is a process to make.
A method for accommodating these materials in the pores is not particularly limited and may be appropriately selected depending on the intended purpose. The hole transport layer, the light emitting layer, and the electron transport layer are laminated in this order. Preferably, for example, the material constituting the molten hole transport layer, the material constituting the light emitting layer, and the material constituting the electron transport layer are formed in this order in the pores. A method of filling the pores with a solution prepared with a solvent that does not dissolve the honeycomb-like porous structure, a method of polymerizing by heating or light irradiation after filling the pores with a monomer, and the like. .
Here, the material constituting the hole transport layer may be accommodated after the conductive layer is deposited in the pores, or may be accommodated directly in the pores without passing through the conductive layer. Also good.
In addition, when the red light emitting material, the green light emitting material, and the blue light emitting material are accommodated, the material constituting the light emitting layer may be accommodated in a mosaic shape in the holes, or color-coded for each predetermined region. Then, it may be filled in a stripe shape, or a section of each colorant may be determined in a predetermined region and accommodated so as to repeat this regularly.

-Other processes-
Examples of the other steps include a cathode forming step of forming a cathode on the honeycomb-like porous structure. The method for forming the cathode is also as already described in the section of the cathode.

  Here, the manufacturing process diagram of the organic EL material according to the present invention is shown in FIG. Preferably, a polymer solution containing a black colorant is cast on the anode surface on the support in the casting step 10 to form a film (hereinafter sometimes referred to as “polymer film”). Thereafter, in the condensation drying step 11, water is condensed and contained as droplets in the polymer film. The condensation drying process 11 will be described in detail later. The solvent and droplets of the polymer solution are evaporated to obtain the honeycomb structure film 12. A filling step 13 is performed in which the hole transport layer, the light emitting layer, and the electron transport layer are stacked in this order in the pores of the honeycomb structure film 12 to obtain the organic EL material 14. In addition, the irradiation process 15 can also be performed while obtaining the organic EL material 14 from a polymer film. In that case, ultraviolet rays or electron beams can be used as irradiation light. Although not shown, a stretching process of stretching a film filled so that a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order in the pores can also be performed.

As the material of the honeycomb structure film 12, a polymer compound that can be dissolved in a water-insoluble solvent as described above (hereinafter also referred to as “hydrophobic polymer compound”) can be preferably used.
Moreover, although the honeycomb structure film 12 can be formed with only the hydrophobic polymer, it is preferable to add an amphiphilic material. As the amphiphilic material, those described above can be appropriately selected and used.
In addition, as the solvent for preparing the polymer solution by dissolving each of the polymer compounds, those described above can be appropriately selected and used.

  Next, FIG. 3 shows a schematic diagram of a film manufacturing facility 20 for manufacturing the honeycomb structure film 12. The polymer solution 21 is placed in a tank 22. The tank 22 is provided with a stirring blade 23, and the polymer solution 21 is uniformly mixed by rotating the stirring blade 23. The polymer solution 21 is sent to the casting die 25 by the pump 24. The casting die 25 is provided on the casting belt 26. Further, the casting belt 26 is stretched around rotating rollers 27 and 28. The rotation belts 27 and 28 are rotated by a driving device (not shown), so that the casting belt 26 travels endlessly. Further, a temperature controller 29 is attached to the rotary rollers 27 and 28. The temperature of the casting belt 26 can be adjusted by adjusting the temperature of the rotating rollers 27 and 28. Further, when the polymer film 40 on the casting belt 26 is peeled off, a peeling roller 30 that supports the polymer film 40 and a winder 31 that winds the polymer film 40 as a film are also provided.

  In the casting step 10, the polymer solution 21 is cast (cast) from the casting die 25 onto the casting belt 26. Subsequently, a condensation drying step 11 is performed. The condensation drying step 11 will be described in conjunction with FIGS. 4A to 4D. As shown in FIG. 4A, a polymer film 40 is formed on the casting belt 26. The surface temperature of the polymer film 40 (hereinafter sometimes referred to as “film surface temperature”) is TL (° C.). In the present invention, the film surface temperature TL is preferably 0 ° C. or higher. If the film surface temperature TL is less than 0 ° C., the droplets in the polymer film 40 may solidify and a desired hole may not be formed.

  The casting chamber in which casting is performed is partitioned into a condensation zone 32 and a drying zone 33 as shown in FIG. The condensation zone 32 is provided with a blower 34. The air 35 adjusted for condensation is blown from the blower 34 to the polymer film 40 on the casting belt 26. As shown in FIG. 3, the blower 34 is preferably composed of a plurality of blower units including blower ports 34a, 34c, 34e and suction ports 34b, 34d, 34f. Thereby, it becomes easy to adjust the dew condensation conditions of the polymer film 40. Note that FIG. 3 shows a structure composed of three units, but the present invention is not limited to the illustrated form.

  A dryer 36 is provided in the drying zone 33. Drying air 37 is blown from the dryer 36 to the polymer film 40. As shown in FIG. 3, it is preferable that the dryer 36 also includes a plurality of air blowing units including air blowing ports 36a, 36c, 36e, and 36g and suction ports 36b, 36d, 36f, and 36h. Thereby, it becomes easy to adjust the drying conditions of the polymer film 40. Although FIG. 3 shows a configuration including four units, the present invention is not limited to the illustrated form.

  It is more preferable to adjust the temperature of the casting belt 26 through the rotary rollers 27 and 28 using the temperature controller 29. Examples of the method for adjusting the temperature include a method in which a liquid flow path is provided inside the rotary rollers 27 and 28 and the heat transfer medium is fed into the liquid flow path for adjustment. In adjusting the temperature, it is preferable that the lower limit value is 0 ° C. or higher. Moreover, it is preferable to set it as the solvent boiling point or less of the polymer solution 21, and, more preferably, to set it as (solvent boiling point -3 degreeC). As a result, the condensed moisture does not solidify and the solvent of the polymer solution 21 is suppressed from rapidly evaporating, so that the honeycomb structure film 12 having an excellent shape can be obtained. Furthermore, in the temperature adjustment, the distribution of the film surface temperature is also within ± 3 ° C. by making the temperature distribution within ± 3 ° C. across the width direction of the polymer film 40. By reducing the temperature distribution in the width direction of the polymer film 40, anisotropy is suppressed in the formation of pores in the honeycomb structure film 12, so that the commercial value is improved.

  Further, it is preferable that the conveying direction of the casting belt 26 is within ± 10 ° with respect to the horizontal direction. By adjusting the transport direction, the form of the droplet 44 can be adjusted as shown in FIGS. By adjusting the form of the droplet 44, the form of the hole can be adjusted.

  Wind 35 is blown from the blower 34. The dew point TD1 (° C.) of the wind 35 is preferably 0 ° C. ≦ (TD1-TL) ° C. with respect to the surface temperature TL (° C.) of the polymer film 40 passing through the condensation zone 32, and 0 ° C. ≦ (TD1-TL) More preferably, the temperature is more preferably from 5 ° C. to 60 ° C., and particularly preferably from 10 ° C. to 40 ° C. When the (TD1-TL) ° C. is less than 0 ° C., condensation may be difficult to occur, and when it exceeds 80 ° C., condensation and drying become steep, and it is difficult to control the pore size and make it uniform. May be. The temperature of the wind 35 is not particularly limited and can be appropriately selected according to the purpose. When the temperature of the wind is less than 5 ° C., the liquid, particularly water, hardly evaporates and the honeycomb structure film 12 having a good shape may not be obtained. Moreover, when it exceeds 100 degreeC, before the droplet 44 arises in the polymer film 40, there exists a possibility of volatilizing as water vapor | steam.

  As shown in FIG. 4A, moisture (modeled) 43 in the wind 35 in the condensation zone 32 is condensed on the polymer film 40 into droplets 44. Then, as shown in FIG. 4B, the moisture 43 is condensed using the droplet 44 as a nucleus to grow the droplet 44. As shown in FIG. 4C, when the drying air 37 is blown to the polymer film 40 in the drying zone 33, the organic solvent 42 is volatilized from the polymer film 40. At this time, water is volatilized also from the droplets 44, but the volatilization rate of the organic solvent 42 is faster. Therefore, the droplets 44 have a substantially uniform shape due to surface tension as the organic solvent 42 volatilizes. Further, as the drying proceeds, moisture evaporates as water vapor 48 from the droplets 44 of the polymer film 40 as shown in FIG. 4D. When the droplet 44 evaporates from the polymer film 40, the portion where the droplet 44 was formed becomes the hole 47, and the honeycomb structure film 12 as shown in FIG. 5 is obtained. In the present invention, the form of the honeycomb structure film 12 is not particularly limited. Specifically, the distance L2 between the adjacent holes 47 can be controlled to 0.05 μm or more and 100 μm or less in the distance between the centers thereof. it can.

  The blowing direction of the wind 35 is parallel to the moving direction of the polymer film 40 (cocurrent flow). When the air is blown as a countercurrent, the film surface of the polymer film 40 may be disturbed, and the growth of the droplets may be hindered. Further, the blowing speed of the wind 35 is preferably 0.1 m / s or more and 20 m / s or less, more preferably 0.5 m / s or more and 15 m / s or less, relative to the moving speed of the polymer film 40, and 2 m / s. More preferably, it is s or more and 10 m / s or less. If the blowing speed is less than 0.1 m / s, the polymer film 40 may be transported to the drying zone 33 without the droplets 44 growing sufficiently in the polymer film 40. Moreover, when it exceeds 20 m / s, there exists a possibility that disorder may arise in the polymer film 40 surface, or condensation may not fully advance.

  The time for the polymer film 40 to pass through the condensation zone 32 is preferably 0.1 seconds or more and 100 seconds or less. If the passage time is less than 0.1 seconds, it may be difficult to form a desired hole because the droplets 44 are formed without being sufficiently grown. There is a possibility that the film becomes too large to obtain a honeycomb structure film.

  The blowing speed of the drying air 37 for drying the polymer film 40 in the drying zone 33 is preferably 0.1 m / s or more and 20 m / s or more, more preferably 0.5 m / s or more and 15 m / s or less, and 2 m / s or more. 10 m / s or less is still more preferable. If the blowing speed is less than 0.1 m / s, the evaporation of moisture from the droplets 44 may not proceed sufficiently, and the productivity may be inferior. If it exceeds 20 m / s, the droplets 44 are inferior. As a result, the evaporation of moisture suddenly occurs and the shape of the formed hole 37 may be disturbed.

  When the dew point of the drying air 37 is TD2 (° C.), the relationship with the film surface temperature TL (° C.) is preferably (TL−TD2) ° C. ≧ 1 ° C. As a result, the growth of the droplet 44 of the polymer film 40 is stopped in the drying zone 33, and the water constituting the droplet can be volatilized as the water vapor 48.

  The air blowing from the blowers 34 and 37 can be dried by a reduced pressure drying method in addition to the method of blowing air with a 2D nozzle. By performing drying under reduced pressure, it is possible to adjust the evaporation rate of the organic solvent 42 and the moisture 43 of the droplets 44. By adjusting this, a droplet 44 is formed in the polymer film 40, the droplet 44 is evaporated while the organic solvent 42 is evaporated, and a hole 47 is formed at a position where the droplet is provided. The size and shape of the holes in the invention can be changed.

  Also, a method of drying by a reduced pressure drying method, or a condenser cooled from the membrane surface and having a groove on the surface at a position about 3 to 20 mm away from the membrane surface, water vapor (volatile organic solvent is also on the surface of the condenser) In addition, a method of condensing and drying can also be applied. By applying any one of the drying methods, the film surface of the polymer film 40 can be dried with less dynamic influence, so that a smoother film surface can be obtained.

  Further, by using a plurality of blower units of the blower 34 and the dryer 36 or by dividing the blower unit into a plurality of zones, different dew point conditions can be set or different drying temperature conditions can be set. By selecting these conditions, it is possible to improve the dimensional controllability of the holes 47 and improve the hole uniformity. The number of blower units and zones is not particularly limited, but an optimal combination is determined in terms of film quality and equipment cost.

  The relationship between the film surface temperature TL (° C.) and the dew point temperature TDn (° C.) of the condensation zone or drying zone (n means the n zone number) shall be 0 ° C. ≦ | TDn−TL | ° C. ≦ 80 ° C. Is preferred. By setting the difference to 80 ° C. or less, rapid volatilization of at least one of the organic solvent and moisture can be suppressed, and the honeycomb structured film 12 having a desired form can be obtained. In addition, when impurities are mixed into the polymer film 40, the formation of the honeycomb structure is hindered. Therefore, it is preferable that the dust levels of the air outlets 34a, 34c, 34e, 36a, 36c, 36e, and 36g be class 1000 or less. Therefore, it is preferable to attach an air conditioner 39 to the housing 38 in which the blower 34 and the dryer 36 are installed, thereby performing air conditioning in the housing 38. Thereby, the possibility that impurities are mixed into the polymer film 40 is reduced, and a good honeycomb structure film 12 can be obtained.

  The honeycomb structure film 12 that has been dried is peeled off from the casting belt 26 while being supported by the peeling roller 30, and wound up by the winder 32. In addition, although the conveyance speed of the honeycomb structure film 12 is not specifically limited, It is preferable that they are 0.1 m / min or more and 60 m / min or less. If the conveyance speed is less than 0.1 m / min, the productivity is inferior and the cost is not preferable. On the other hand, if it exceeds 60 m / min, an excessive tension is applied to the honeycomb structure film when it is transported, causing a defect such as a disorder of the honeycomb structure. The honeycomb structured film 12 can be continuously manufactured by the above method.

  FIG. 6 shows a film manufacturing facility 60 according to another embodiment of the present invention. A film 62 serving as a support is conveyed from the delivery device 61. The film 62 is conveyed while being wound around the backup roller 63. A slide coater 64 is provided facing the backup roller 63. The slide coater 64 is provided with a decompression chamber 65. A polymer solution 67 sent from a polymer solution supply device 66 by a liquid feed pump is pushed out from a slide coater 64 and applied onto a film 62 as a support, whereby a polymer film 68 is formed.

  The slide coater 64 is excellent in uniform coating properties in the transport direction of the film 62 and can form the polymer film 68 at a high speed. Further, even when the surface of the film 62 as a support is uneven, the film 62 is smoothed when it is wound around the backup roller 63, so that it is excellent in uniform coatability. Furthermore, since the coating is performed in a non-contact manner on the film 62, uniform coating is possible without damaging the surface of the film 62.

  The polymer film 68 formed on the film 62 is subjected to the condensation drying process 11 by the wind 70 of the blower 69. In addition, the description of the part of the same conditions as the description mentioned above is abbreviate | omitted in the condensation drying process 11. After passing through the condensation drying step 11, the honeycomb structure film 71 is wound around the winding roll 72. Further, the film 62 is also taken up by the take-up roll 73. The transport direction of the film 62 on which the polymer film 68 is formed is preferably within ± 10 ° with respect to the horizontal direction. In addition, it is more preferable to use a film 62 made of a material that easily absorbs the organic solvent of the polymer solution 66. These materials are not particularly limited as long as they absorb an organic solvent. For example, when methyl acetate is used as the main solvent of the polymer solution 67, it is preferable to use cellulose acylate as the material of the film.

  In FIG. 7, the film manufacturing equipment 80 of other embodiment used for the manufacturing method of the film which concerns on this invention is shown. In addition, description of the same location as the film manufacturing equipment 60 is abbreviate | omitted. A film 82 serving as a support is conveyed from the delivery machine 81. The film 82 is conveyed while being wound around the backup roller 83. A multi-layer slide coater 84 is provided opposite to the backup roller 83. The multilayer slide coater 84 is provided with a decompression chamber 85. A polymer solution 87 sent from a polymer solution supply device 86 by a liquid feed pump is pushed out from a multilayer slide coater 84 and applied onto a film 82 as a support to form a polymer film 88. . The polymer film 88 formed on the film 82 is subjected to the condensation drying process 11 by the wind 90 of the blower 89. After passing through the condensation drying step 11, the honeycomb structure film 91 is wound around a winding roll 92. Further, the film 82 is also taken up by the take-up roll 93.

  By casting (applying) the polymer solution 87 composed of multiple layers onto the film 82, it is possible to change the form, physical properties, and the like in the thickness direction of the honeycomb structure film 91.

  In FIG. 8, the film manufacturing equipment 100 of other embodiment used for the manufacturing method of the film which concerns on this invention is shown. In addition, description of the same location as the film manufacturing equipment 60 is abbreviate | omitted. A film 102 serving as a support is conveyed from the delivery machine 101. The film 102 is conveyed while being wound around the backup roller 103. An extrusion coater 104 is provided facing the backup roller 103. The extrusion coater 104 is provided with a decompression chamber 105. The polymer solution 107 sent from the polymer solution supply device 106 by the liquid feed pump is pushed out from the extrusion coater 104 and applied onto the film 102 as the support, thereby forming the polymer film 108. . The polymer film 108 formed on the film 102 is subjected to the condensation drying process 11 by the wind 110 of the blower 109. After passing through the condensation drying step 11, the honeycomb structure film 111 is wound around the winding roll 112. Further, the film 102 is also taken up by the take-up roll 113.

  In FIG. 9, the film manufacturing equipment 120 which manufactures the film which concerns on this invention is shown and demonstrated. The polymer solution 122 is applied to the film 123 using a wire bar applicator 121. The wire bar 124 that rotates in the moving direction of the film 123 that moves at a constant speed pulls the polymer solution 122 from the primary polymer solution tank 125 to the liquid storage portion 126 by the rotation. When the polymer solution 122 in the liquid storage portion 126 comes into contact with the film 123 via the wire bar 124, a polymer film 127 having a uniform thickness is formed. The polymer film 127 is subjected to the condensation drying step 11 with the wind 129 of the blower 128, whereby the honeycomb structure film 130 can be obtained. In the manufacturing method of the honeycomb structure film 130 using the wire bar 124, the liquid storage portion 126 prevents air from entering the contact portion between the polymer solution 122 and the film 123, so that bubbles are mixed into the polymer film 127. There is an advantage that it becomes difficult.

  When the films 62, 82, 102, and 123 are used as the support, the honeycomb structure films 71, 91, 111, and 130 can be wound as an integral film and used as the base film of the organic EL material 14.

  FIG. 10 shows a production facility 140 for producing a film according to the present invention. The film 141 is conveyed while being wound around the impression cylinder 142. A plate cylinder 143 is disposed opposite the impression cylinder 142. A desired pattern is formed on the surface of the plate cylinder 143. The polymer solution 145 stored in the polymer solution tank 144 is accumulated in the recess as the plate cylinder 143 rotates. Excess polymer solution 145 is scraped off by the doctor blade 146. Thereafter, a polymer solution 145 is applied on the film 141 that is wound around the impression cylinder 142 and a polymer film 147 is formed.

  The condensation drying process 11 of the polymer film 147 is performed by the blower 148. The wind 149 blown from the blower 148 is a parallel flow in the same direction as the transport direction of the film 141. In the polymer film 147, the honeycomb structure 150 is formed through the condensation drying step 11. The film 141 becomes the honeycomb structure forming film 151 in which the honeycomb structure 150 is formed in a desired pattern.

  The organic EL material of the present invention obtained according to the method of manufacturing the organic EL material of the present invention may be used as it is by manufacturing it on a desired support from the beginning, or immersed in a suitable solvent such as ethanol. After being peeled off from the support at the time of production, it may be installed on a desired substrate and used. In the case of use after peeling, an adhesive such as an epoxy resin or a silane coupling agent suitable for the material and the material of the desired substrate may be used for the purpose of improving the adhesion to a new substrate.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
On a PEN (polyethylene naphthalate) substrate as a support, a barrier layer in which 5 layers of organic and inorganic layers are laminated by the method described in US Patent Application Publication No. 2005/0112378 is installed, and a mask is formed thereon. Was used to pattern 100 μm wide indium tin oxide (ITO) to form an anode. Next, polystyrene having a weight average molecular weight of 45,000 and an amphiphilic polymer represented by the following structural formula having a weight average molecular weight of 50,000 as a fine pore structure material on the substrate is 10 by mass ratio. : Carbon black (Mitsubishi Chemical Corporation, Mitsubishi # 2770B) as a black colorant is added to 0.5 mL of methylene chloride solution (0.1% by mass as a polymer concentration) mixed at a ratio of 1: 1 The coating solution was prepared by adding 2% by mass with respect to the amount. The glass transition temperature (Tg) of the PEN substrate was 120 ° C. when measured with a differential thermal balance (manufactured by Rigaku). The water vapor permeability of the PEN substrate was 1.0 × 10 ⁻³ g / m ² · 24 h as measured by the MOCON method.
Next, the entire volume is developed on a glass substrate for HDD kept at 2 ° C. in a closed space not affected by outside air, and constant humidity of 70% relative humidity is 45 ° with respect to the substrate surface at a steady flow rate of 2 L / min. A uniform honeycomb structure was obtained by spraying from the direction of and evaporating methylene chloride. The constant humidity air was supplied by connecting a humidity generator manufactured by Yamato Scientific Co., Ltd. to a compressor SC-820 manufactured by Hitachi Koki Co., Ltd., on which a commercially available dust removal air filter (filtration degree 0.3 μm) was installed. Moreover, it was 0.3 m / s when the flow velocity of the air of a spraying part was measured.

  When the structure of the obtained film was observed with a field emission scanning electron microscope (manufactured by Hitachi, Ltd.), a honeycomb structure in which pores having a pore diameter of 10 μm were regularly arranged in a hexagonal shape could be confirmed. The vacancies formed a single layer from the front surface to the back surface of the film, and the structure was such that the top and bottom of the film penetrated. The vacancies were distributed over almost the entire surface except for a part around the cast area, and had a beautiful spherical shape.

Next, the hole transport material, the light emitting material, and the electron transport material are filled in the pores of the obtained film by discharging them in this order from the inkjet nozzle, and the hole transport layer, the light emitting layer, After preparing the laminated body laminated | stacked in order of the electron carrying layer, the lithium fluoride (LiF) and aluminum (Al) layer as a cathode are formed in a 100 micrometer width using a mask in the orthogonal | vertical direction with ITO, Example 1 An organic EL material was prepared.
Here, N, N′-diphenyl-N, N′-dinaphthylbenzidine is used as a material constituting the hole transport layer, and octaethylporphyin is used as a red light emitting material as a material constituting the light emitting layer. Complex, green light-emitting material, tris (phenylpyridine) Ir complex, blue light-emitting material, bis [(4,6-fluorophenyl) -pyridinate-N, C2 ′] picolinate complex as a material constituting the electron transport layer Used the compounds described in Example 2 of US Patent Application Publication No. 2005/112378. The light emitting materials of the respective colors were filled in a mosaic shape.
When the organic EL material was caused to emit light, extremely good light emission was obtained without using a complicated process such as a photoresist.

(Example 2)
Using triphenyldiamine (TPD) as a hole transport material and aluminum quinolinol complex (Alq ₃ ) as a light emitting material, a laminate is prepared by vapor deposition in a vacuum chamber, and after forming a cathode, an epoxy material is used. An organic EL material of Example 2 was produced in the same manner as in Example 1 except that the whole was sealed with a glass plate.
When the organic EL material was caused to emit light, as in Example 1, good light emission was recognized without using a complicated process such as a photoresist.

(Example 3)
In Example 1, the same procedure as in Example 1 was used, except that polyvinylcarbazole (molecular weight 63,000, manufactured by Aldrich) and tris (2-phenylpyridine) iridium complex were used at 40: 1 as materials constituting the color developing layer. Thus, an organic EL material of Example 3 was produced.
When the organic EL material was caused to emit light, as in Example 1, good light emission was recognized without using a complicated process such as a photoresist.

Example 4
In Example 1, except that two layers of organic and inorganic were laminated on the PEN substrate, and a water vapor permeable 5 × 10 ⁻² g / m ² · 24 h substrate was used as the PEN substrate. In the same manner as in Example 1, the organic EL material of Example 4 was produced.

(Example 5)
In Example 1, the organic EL material of Example 5 was produced in the same manner as in Example 1 except that a PET (polyethylene terephthalate) substrate was used as the support instead of the PEN substrate. The glass transition temperature (Tg) of the PET substrate was 85 ° C. as measured by a differential thermal balance (manufactured by Rigaku). The water vapor permeability of the PET substrate was 5 × 10 ⁻¹ g / m ² · 24 h as measured by the MOCON method.

(Example 6)
In Example 1, a methylene chloride solution in which polystyrene having a weight average molecular weight of 45,000 and an amphiphilic polymer represented by the following structural formula having a weight average molecular weight of 50,000 were mixed at a mass ratio of 95: 5 ( The organic EL material of Example 6 was produced in the same manner as in Example 1 except that the black colorant was added to 0.5 mL of the polymer concentration (0.2% by mass as a polymer concentration) to prepare a coating solution.

(Example 7)
In Example 1, except that a black colorant was added to 0.5 mL of a methylene chloride solution (0.2% by mass as a polymer concentration) in which only polystyrene having a weight average molecular weight of 45,000 was dissolved, and a coating solution was prepared. The organic EL material of Example 7 was produced in the same manner as Example 1.

(Example 8)
In Example 1, a black colorant was added to 0.5 mL of a methylene chloride solution (polymer concentration: 0.2% by mass) in which only an amphiphilic polymer represented by the following structural formula was dissolved to prepare a coating solution. Except for this, the organic EL material of Example 8 was produced in the same manner as Example 1.

(Comparative Example 1)
According to the method described in Example 1 of JP-A-2005-240011, an organic EL material of Comparative Example 1 was produced.

(Comparative Example 2)
An organic EL material of Comparative Example 2 was produced according to the method described in Comparative Example 2 of US Patent Application Publication No. 2005/112378.

<Evaluation>
The following evaluation was performed using the obtained organic EL materials of Examples 1 to 8 and Comparative Examples 1 and 2.

(1) Evaluation of durability The surface area of the non-light-emitting part of the obtained organic EL material was measured immediately after production and after standing for 14 days at 60 ° C. and 90% RH. After calculating the value obtained by subtracting the area of the light emitting part as the area of the light emitting part, the area is determined by (light emitting part area after standing for 14 days at 60 ° C. and 90% RH) / (light emitting part area immediately after production) × 100. Value (%) was evaluated as an index of durability. It means that durability is so high that this value is large.
In addition, the said non-light-emission part measured by making the location which light emission is not seen at all into a non-light-emission part visually. The results are shown in Table 1.

(2) Evaluation of fineness After the obtained organic EL material was allowed to stand at 60 ° C. and 90% RH for 14 days, the fineness was evaluated using an electron microscope (manufactured by Hitachi, Ltd.). In the organic EL materials of Examples 1 to 8, the same fineness as that obtained when a conventionally known lithography was used was obtained.

From the results of Table 1, in the organic EL materials of Examples 1 to 8, compared to the organic EL material of the comparative example, (light emitting part area after being left for 14 days at 60 ° C. and 90% RH) / (production It was found that the value (%) obtained by the immediately following light emitting part area) × 100 was large and the durability was high. In particular, in the organic EL materials of Examples 1 to 3, the value (%) obtained by (light emitting part area after standing for 14 days at 60 ° C. and 90% RH) / (light emitting part area immediately after production) × 100 It was found that the durability was extremely high.

The organic EL material of the present invention does not require an unnecessary component for light emission, has excellent durability, and has high definition. For example, a computer, an on-vehicle display, an outdoor display, a household device, a commercial use It can be suitably used in various fields including equipment, home appliances, traffic-related indicators, clock indicators, calendar indicators, luminescent screens, audio equipment, and the like.
The organic EL material manufacturing method of the present invention can be suitably used for manufacturing the organic EL material of the present invention because the organic EL material can be manufactured by a simple method without providing a partition layer using photolithography or the like. .

FIG. 1 is a schematic view showing an example of the organic EL material of the present invention. FIG. 2 is a process diagram illustrating an example of a method for producing an organic EL material according to the present invention. FIG. 3 is a schematic view of a film production facility used in an example of a method for producing an organic EL material according to the present invention. FIG. 4A is a schematic diagram illustrating an example of a method for forming an organic EL material according to the present invention, in which a polymer film is formed on a casting belt. FIG. 4B is a schematic diagram illustrating an example of a method for forming an organic EL material according to the present invention, in which droplets are condensed and grow. FIG. 4C is a schematic diagram illustrating an example of a method for forming an organic EL material according to the present invention, in which an organic solvent is volatilized from a polymer film by drying. FIG. 4D is a schematic diagram showing an example of a method for forming the organic EL material of the present invention, and a state in which moisture is volatilized from the droplets of the polymer film by drying. FIG. 5 is a cross-sectional view showing an example of the organic EL material according to the present invention. FIG. 6 is a schematic view of a film production facility showing another example used in the method for producing an organic EL material according to the present invention. FIG. 7 is a schematic view of a film production facility showing still another example used in the method for producing an organic EL material according to the present invention. FIG. 8 is a schematic view of a film production facility showing still another example used in the method for producing an organic EL material according to the present invention. FIG. 9 is a schematic view of a film production facility showing still another example used in the method for producing an organic EL material according to the present invention. FIG. 10 is a schematic view of a film production facility showing still another example used in the method for producing an organic EL material according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Cast process 11 Condensation drying process 12 Honeycomb structure film 13 Filling process 14 Organic EL material

Claims (9)

  Between the anode and the cathode on the support, it has a fine hole structure, and a hole transport layer, a light emitting layer, and an electron transport layer are provided in this order in at least one hole in the fine hole structure. An organic EL material characterized by comprising:   The organic EL material according to claim 1, wherein the fine pore structure is a honeycomb-like porous structure produced by self-organization.   3. The organic EL material according to claim 1, wherein any one of a red light emitting material, a green light emitting material, and a blue light emitting material is contained in at least one hole in the fine hole structure.   The organic EL material according to any one of claims 1 to 3, wherein the fine pore structure material is at least one selected from a hydrophobic polymer and an amphiphilic polymer.   The organic EL material according to claim 1, wherein the fine pore structure material contains a black colorant.   The organic EL material according to claim 1, wherein the support is a film having a glass transition temperature (Tg) of 120 ° C. or higher. The organic EL material according to claim 6, wherein the film has a water vapor permeability of 1 × 10 ⁻³ g / m ² · 24 h or more. A coating liquid containing an organic solvent and a polymer compound is applied to the anode surface on the support, droplets are formed in the obtained film, and the organic solvent and the droplets are evaporated to enter the film. A microporous structure manufacturing process for manufacturing a microporous structure having pores;
And a containing step of containing a hole transport layer, a light emitting layer, and an electron transport layer so as to be laminated in this order in the pores of the obtained fine pore structure. Method. The method for producing an organic EL material according to claim 8, wherein the coating liquid contains a black colorant.