WO2012026193A1

WO2012026193A1 - Substrate for organic electroluminescence and organic electroluminescent device

Info

Publication number: WO2012026193A1
Application number: PCT/JP2011/064170
Authority: WO
Inventors: 飛世　学; 慎一郎園田; 静波李; 英正細田
Original assignee: 富士フイルム株式会社
Priority date: 2010-08-23
Filing date: 2011-06-21
Publication date: 2012-03-01
Also published as: JP5912306B2; JP2012069507A

Abstract

The purpose of the present invention is to obtain: a substrate for organic electroluminescence, in which a fine particle layer is formed on one surface of a base, and which is capable of suppressing spectrum modulation, surface position dependence of chromaticity and angle dependence of chromaticity due to interference of a barrier layer that is provided on the other surface of the base and is also capable of improving the light extraction efficiency; and an organic electroluminescent device which comprises the substrate for organic electroluminescence. In order to accomplish the purpose, a substrate for organic electroluminescence comprising at least a barrier layer that has a thickness unevenness of 10-1,000 nm (inclusive) and a fine particle layer that contains fine particles is provided.

Description

Organic electroluminescent substrate and organic electroluminescent device

The present invention relates to an organic electroluminescent substrate and an organic electroluminescent device using the organic electroluminescent substrate.

Organic electroluminescent devices are self-luminous display devices and are expected to be used for displays and lighting. For example, an organic electroluminescent display has advantages in display performance such as higher visibility than conventional CRTs and LCDs and no viewing angle dependency. In addition, there is an advantage that the display can be made lighter and thinner. On the other hand, in addition to the advantages that organic electroluminescence lighting can be reduced in weight and thickness, it has the potential to realize illumination in a shape that could not be realized by using a flexible substrate. Yes.

In such an organic electroluminescent device, in order to improve the light extraction efficiency, many proposals have been made to provide a light extraction layer.
For example, Patent Document 1 proposes a light emitting device having a barrier layer on one surface of a base material and a high refractive index uneven layer on the other surface of the base material. Paragraph [0008] of this proposal states that the high refractive index uneven layer may be a fine particle layer.
However, the proposed high refractive index uneven layer has little angle dependency of chromaticity change, and cannot sufficiently suppress spectrum modulation and angle dependency. Further, even in light extraction, a simple uneven layer is less effective, there is a variation in the formation of the uneven layer, and there is a possibility that the light extraction efficiency and the angle dependency of chromaticity change may also vary. Furthermore, in this proposal, since the outermost surface on the light extraction side is not flat, there is a problem that foreign matter is easily attached, and light extraction efficiency is reduced due to shielding by the foreign matter.

Therefore, it is possible to provide a fine particle layer on one surface of the substrate, and suppress spectral modulation due to interference of a barrier layer provided on the other surface of the substrate, surface position dependency of chromaticity, and angle dependency of chromaticity. In addition, it is currently desired to provide an organic electroluminescent substrate capable of enhancing the light extraction efficiency and an organic electroluminescent device having the organic electroluminescent substrate.

JP 2004-20746 A

This invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, according to the present invention, a fine particle layer is provided on one surface of a substrate, spectrum modulation due to interference of a barrier layer provided on the other surface of the substrate, surface position dependency of chromaticity, and angle dependency of chromaticity. It is an object of the present invention to provide an organic electroluminescence substrate capable of suppressing the property and increasing the light extraction efficiency, and an organic electroluminescence device having the organic electroluminescence substrate.

Means for solving the problems are as follows. That is,
<1> An organic electroluminescence substrate comprising at least a barrier layer having a thickness unevenness of 10 nm to 1,000 nm and a fine particle layer containing fine particles.
<2> The organic electroluminescence substrate according to <1>, wherein the barrier layer has a multilayer structure in which an organic layer made of an organic material and an inorganic layer made of an inorganic material are alternately laminated.
<3> The organic electroluminescent substrate according to <2>, wherein the total number of stacked organic layers and inorganic layers is 2 or more.
<4> The organic electroluminescent element substrate according to any one of <1> to <3>, wherein the fine particles have an average particle diameter of 0.5 μm to 10 μm.
<5> The organic electroluminescent substrate according to any one of <1> to <4>, wherein the fine particle distribution density in the fine particle layer is 30% to 80%.
<6> The organic electroluminescence substrate according to any one of <1> to <5>, wherein the light emission surface of the fine particle layer is flat or has a planarization layer on the light emission surface of the fine particle layer.
<7> The organic electroluminescence substrate according to any one of <1> to <6>, further comprising a base material, wherein the material of the base material is any one of polyethylene terephthalate and polyethylene naphthalate. is there.
<8> An organic electroluminescent device comprising the organic electroluminescent substrate according to any one of <1> to <7>.
<9> The chromaticity of the organic electroluminescence substrate before the fine particle layer is provided in the CIE color system in which the chromaticity x is 0.01 to 0.05 and the chromaticity y is 0.00 from the target chromaticity. The organic electroluminescent device according to <8>, wherein the organic electroluminescent device is set to be larger by 01 to 0.05.

Due to the interference effect of the barrier layer provided on the base material (especially when the refractive index of the barrier layer and the base material is different), the emission spectrum from the organic electroluminescent layer provided on the barrier layer is modulated, and in particular, multilayering In the barrier layer, the modulation is strong and the chromaticity may change. When such uneven thickness of the barrier layer occurs between batches, the chromaticity shifts between batches. Further, when there is uneven thickness (position dependency) of the barrier layer, the chromaticity changes depending on the light emission location.
On the other hand, a change in chromaticity may increase due to a change in interference length due to angle dependency. In particular, in the case of white light emission, the color balance changes, so that the white color changes greatly and the appearance changes depending on the angle, resulting in an uncomfortable feeling. If the influence of the barrier layer is added to such an angle dependency, the change in chromaticity may further increase.
Therefore, in the organic electroluminescent device of the present invention, by using an organic electroluminescent substrate having at least a barrier layer having a thickness unevenness of 10 nm to 1,000 nm and a fine particle layer containing fine particles, Spectral modulation due to interference of the barrier layer provided on one surface, surface position dependency of chromaticity, and angle dependency of chromaticity can be suppressed, and light extraction efficiency provided on the other surface of the substrate can be improved. Can do.

According to the present invention, conventional problems can be solved, and a fine particle layer is provided on one surface of a base material, and spectrum modulation and chromaticity surface position due to interference of a barrier layer provided on the other surface of the base material. It is possible to provide an organic electroluminescence substrate capable of suppressing the dependency and the angle dependency of chromaticity and increasing the light extraction efficiency, and an organic electroluminescence device having the organic electroluminescence substrate.

FIG. 1 is a schematic view showing an organic electroluminescent device of Example 1. FIG. 2 is a schematic view showing an organic electroluminescent device of Example 2. FIG. 3 is a schematic view showing an organic electroluminescent device of Example 3. FIG. 4 is a schematic view showing an organic electroluminescent device of Example 4. FIG. 5 is a schematic view showing an organic electroluminescent device of Comparative Example 1. FIG. 6 is a schematic view showing an organic electroluminescent device of Comparative Example 2. FIG. 7 is a schematic view showing an organic electroluminescent device of Comparative Example 3. FIG. 8 is a schematic view showing an organic electroluminescent device of Comparative Example 4. FIG. 9 is a schematic view showing an organic electroluminescent device of Comparative Example 5. FIG. 10 is a schematic view showing an organic electroluminescent device of Application Example 1. FIG. 11 is a schematic view showing an organic electroluminescent device of Application Example 2. FIG. 12 is a graph showing an emission spectrum without a barrier layer (Comparative Example 1). FIG. 13 is a graph showing an emission spectrum with a barrier layer (Comparative Example 4). FIG. 14 is a graph showing an emission spectrum of a barrier layer and a concavo-convex layer (Comparative Example 5). FIG. 15 is a graph showing an emission spectrum of a barrier layer and a fine particle layer (Example 4). FIG. 16 is a graph showing the difference in emission spectrum between Comparative Example 4-1 and Comparative Example 4-2, which are organic electroluminescence devices having the same configuration as Comparative Example 4 and simultaneously manufactured with a barrier layer. FIG. 17 is a diagram illustrating a state in which a substrate with a barrier layer is cut and a sample is manufactured in the example.

(Organic electroluminescent substrate)
The substrate for organic electroluminescence of the present invention has at least a barrier layer and a fine particle layer, and has a base material and, if necessary, other layers.

Examples of the organic electroluminescence substrate include a base material, a mode having a barrier layer on one surface of the base material, and a fine particle layer on the other surface of the base material, that is, the barrier layer is a base material. It is preferable to be provided on the surface of the organic electroluminescent layer, and the fine particle layer is provided on the surface of the substrate on the light emission side.

<Barrier layer>
The barrier layer has a thickness unevenness of 10 nm to 1,000 nm, and preferably 10 nm to 800 nm. If the thickness unevenness is less than 10 nm, the change in chromaticity of the organic electroluminescence device due to the thickness unevenness becomes almost inconspicuous, and the effect of averaging the chromaticity by the fine particle layer may not appear. On the other hand, if the thickness unevenness exceeds 1,000 nm, it exceeds the wavelength of visible light emitted from the organic electroluminescent layer, and chromaticity change due to the interference effect is less likely to occur, as in the case where the thickness unevenness is less than 10 nm. The effect of averaging the chromaticity due to the fine particle layer may be difficult to appear.
Here, the uneven thickness of the barrier layer means a maximum height difference in the thickness direction of the barrier layer on one substrate.
When the barrier layer is an organic layer formed by applying an organic material, the thickness unevenness is about 60 nm, and when the barrier layer is an inorganic layer formed by vapor deposition or sputtering of an inorganic material The thickness unevenness is about 15 nm.
The average thickness of the barrier layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the organic layer is preferably 300 nm to 2,000 nm, and more preferably 800 nm to 1,500 nm. In the case of the inorganic layer, 10 nm to 200 nm is preferable, and 30 nm to 150 nm is more preferable.
The thickness unevenness of the barrier layer can be determined, for example, by cutting a part of the produced barrier layer and measuring the thickness with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Co., Ltd.).

The barrier layer may be an organic layer made of an organic material alone or an inorganic layer made of an inorganic material alone, but a multilayer in which organic layers made of an organic material and inorganic layers made of an inorganic material are alternately laminated. It is preferable to have a structure in terms of preventing peeling due to stress relaxation of the inorganic layer, filling pinholes generated in the inorganic layer, and preventing an increase in moisture permeability and oxygen permeability.
The total number of stacked and the organic layer and the inorganic layer is preferably more than one layer, four layers and 11 layers and more preferably. When the total number of stacked layers is less than 2, the barrier layer has increased water permeability and oxygen permeability due to pinholes, affecting the organic electroluminescent device, and generating dark spots, in the worst case May not be lit.

-Inorganic layer-
At least one of the inorganic layers is preferably composed of two or more kinds of metal oxides.
Such inorganic layers can be formed by co-deposition on the film two or more kinds of metal oxides.
Examples of the metal oxide include, but are not limited to, oxides such as Si, Al, In, Sn, Zn, Ti, Cu, Ce, and Ta. From light transmittance aspect when forming the cost and film, preferably, silicon oxide and aluminum oxide.

As a method for forming these oxide thin films, for example, known methods such as sputtering, vacuum deposition, ion plating, and plasma CVD can be used. in that the deposition while at the same time, the reactive sputtering method, an electron beam evaporation method and a combined method thereof are particularly preferred.
In the reactive sputtering method, for example, metal targets of Si and Al are installed on two electrodes, respectively, and a rare gas such as argon and oxygen gas are introduced in a high vacuum, while metal atoms are introduced by DC plasma and high frequency plasma. It is a method of knocking out and co-depositing while reacting metal atoms and oxygen on the film surface.
The electron beam heating vapor deposition method is a method in which a crucible containing Si or SiOx and a crucible containing Al or Al ₂ Ox are placed in a vacuum chamber, heated and evaporated by an electron beam, and co-deposited on the film surface. It is. In this case, oxygen gas may or may not flow depending on the degree of oxidation of the material placed in the crucible and the target degree of oxidation of the film.

The ratio of the two metals in the co-deposited oxide thin film can be arbitrarily set, but is preferably in the range of 1/9 to 9/1. In the case of silicon oxide and aluminum oxide, the Si / Al ratio is preferably in the range of 7/3 to 2/8.
In addition, the ratio of each metal atom and oxygen atom is arbitrary, but when the oxygen atom ratio is extremely small from the stoichiometric ratio of the oxide, the transparency of the film is lowered or coloring occurs. It is not preferable. If the contrary is an oxygen atom too many also not preferable because the barrier is lowered density of the film is lowered. In the case of SiOx, the value of x is particularly preferably 1.5 to 1.8. In the case of Al ₂ Ox, the value of x is particularly preferably 1.0 to 1.4.
If the thickness of the inorganic layer is too thin, the barrier property becomes insufficient. Conversely, if the thickness is too thick, the barrier property is remarkably impaired by cracking or breaking when bent. Therefore, the appropriate thickness of the inorganic layer is preferably 5 nm to 1,000 nm, more preferably 10 nm to 1000 nm, and still more preferably 10 nm to 200 nm.

-Organic layer-
The organic layer can be any polymer. Examples of preferable organic layers and methods for forming the organic layers will be described below.

(1) Polysiloxane A vapor obtained by heating and evaporating hexamethyldisiloxane is introduced into a parallel plate type plasma device using an RF electrode to cause a polymerization reaction in the plasma and deposited as a polysiloxane thin film on the film substrate. Let High film formation speed, no polymerization initiator required, easy hydrophilization with oxygen plasma, etc., good adhesion to the inorganic layer applied afterwards, bending resistance when used as a laminated barrier film It has characteristics such as excellentness and is particularly preferable.

(2) Polyparaxylylene The raw material diparaxylylene is heated and evaporated in a high vacuum, and this vapor is heated at 650 ° C. to 700 ° C. to thermally decompose to generate thermal radicals. When this radical monomer vapor is introduced into the chamber, the radical polymerization reaction proceeds simultaneously with the adsorption to the film substrate, and is deposited as polyparaxylylene. The feature of this film is that a film having excellent mechanical, thermal and chemical strength is formed, and this method is also a preferable method for the present invention.

(3) Polyaddition polymer It is a polymer that can be obtained by repeated addition polymerization of two types of A and B monomers evaporated in a vacuum alternately in A and B. For example, low molecules such as water and alcohol are not desorbed unlike polycondensation, which is basically excellent as a method for forming a barrier film in a vacuum as in the present invention.
Examples of the polyaddition polymer include polyurethane (diisocyanate / glycol), polyurea (diisocyanate / diamine), polythiourea (dithioisocyanate / diamine), polythioether urethane (bisethyleneurethane / dithiol), and polyimine. (Bisepoxy / primary amine), polypeptide amide (bisazolactone / diamine), polyamide (diolefin / diamide) and the like. Among these, polyurea is particularly preferable in consideration of transparency, material cost, and the like.

(4) Acrylic polymer The acrylic polymer has characteristics such as high curing speed, easy curing at room temperature, and high transparency, and is preferably used as the organic layer.
As the acrylate monomer, there are monofunctional, bifunctional, and polyfunctional, and any of them can be used, but blending is preferable in order to obtain an appropriate evaporation rate, degree of curing, curing rate, and the like. Examples of the monofunctional acrylate include aliphatic, alicyclic, ether-based, cyclic ether-based, aromatic-based, hydroxyl group-containing, and carboxy group-containing, and any of them can be used.

(5) Photocationic curing polymer The cationic polymerization system is characterized by being less irritating compared to the same photocurable acrylate. In particular, ring-opening polymerization types such as epoxy-based and oxetane-based are particularly preferable in the present invention because the volumetric shrinkage during curing is small and the internal stress is small and the adhesiveness is excellent.
As the epoxy system, an alicyclic epoxy system is particularly preferable, and a bifunctional monomer, a polyfunctional oligomer, or a mixture thereof can be preferably used.
The oxetane is preferably a monofunctional oxetane, a bifunctional oxetane, an oxetane having a silsesquioxane structure, or the like. However, a mixture thereof, a mixture to which a glycidyl ether compound is added, or a mixture with an epoxy compound is also preferred.
In the case of a photocationically curable polymer, a photocurable latent curing agent that initiates a curing reaction using light as a trigger may be included. In the case of epoxy type and oxetane type, a photoacid generator is usually preferred. As the photoacid generator, aryl diazonium salts, diaryl iodonium salts and the like are known, and triarylsulfonium salts are the most common.
Moreover, the combined use of the compound which produces | generates a photoradical as a sensitizer is preferable. Examples of the sensitizer include aromatic ketone, phenothiazine, diphenylanthracene, rubrene, xanthone, thioxanthone derivatives, and chlorothioxanthone. Among these, thioxanthone derivatives are preferable.

<Fine particle layer>
The fine particle layer contains at least a polymer and fine particles, and further contains other components as necessary.

<< Fine particle >>
The fine particles are not particularly limited as long as the refractive index is different from the refractive index of the polymer of the fine particle layer, and can scatter light, and can be appropriately selected according to the purpose. It may be inorganic fine particles, and preferably contains two or more fine particles. Hereinafter, it may be referred to as scattering fine particles.

Examples of the organic fine particles include polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, polystyrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads, and the like.
Examples of the inorganic fine particles include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , and the like. Among these, TiO ₂ , ZrO ₂ , ZnO, and SnO ₂ are particularly preferable.

The refractive index of the fine particles is not particularly limited as long as it is different from the refractive index of the polymer of the fine particle layer, and can be appropriately selected according to the purpose, but is preferably 1.55 to 2.6. 58 to 2.1 is more preferable.
The refractive index of the fine particles is determined by measuring the refractive index of the refractive liquid using, for example, an automatic refractive index measuring device (KPR-2000, manufactured by Shimadzu Corporation), and then using a precision spectrometer (GMR-1DA, Shimadzu Corporation). (Manufactured by Seisakusho Co., Ltd.) and can be measured by the Shribsky method.

The average particle size of the fine particles is preferably 0.5 μm to 10 μm, and more preferably 0.5 μm to 6 μm. When the average particle diameter of the fine particles exceeds 10 μm, most of the light is forward scattered, and the ability to convert the angle of light by the fine particles for scattering may be reduced. On the other hand, if the average particle size of the fine particles is less than 0.5 μm, the wavelength becomes smaller than the wavelength of visible light, Mie scattering changes to the Rayleigh scattering region, the wavelength dependency of the scattering efficiency of the fine particles increases, and light emission It is expected that the chromaticity of the element will change greatly and the light extraction efficiency will decrease.
The average particle diameter of the fine particles can be measured, for example, by an apparatus using a dynamic light scattering method such as Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., or by image processing of an electron micrograph.

The volume filling rate of the fine particles in the fine particle layer is preferably 30% to 80%, more preferably 40% to 70%. If the volume filling factor is less than 30%, the probability that the light incident on the fine particle layer is scattered by the fine particles is small, and the ability to convert the light angle of the fine particle layer is small. If it is not thickened, the light extraction efficiency may decrease. Further, increasing the thickness of the fine particle layer leads to an increase in cost, resulting in a large variation in the thickness of the fine particle layer, which may cause a variation in the scattering effect in the light emitting surface. On the other hand, when the volume filling rate exceeds 80%, the surface of the fine particle layer is greatly roughened, and cavities are generated inside, whereby the physical strength of the fine particle layer may be lowered.
The volume filling rate of the fine particles in the fine particle layer can be measured, for example, by a gravimetric method. First, the specific gravity of the particles is measured with a particle specific gravity measuring device (MARK3, manufactured by Union Engineering Co., Ltd.), and the weight of the fine particles is measured with an electronic balance (FZ-3000i, manufactured by A & D). Next, a part of the produced fine particle layer is cut out, and the thickness of the fine particle layer is measured with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Co., Ltd.) to obtain the volume filling rate of the fine particles in the fine particle layer. it can.

-High refractive index fine particles-
The high refractive index fine particles preferably have a refractive index of 2.0 or more, more preferably 2.4 to 3.0. The average primary particle size is preferably 0.5 nm to 100 nm, more preferably 1 nm to 80 nm, and even more preferably 1 nm to 50 nm.
If the refractive index of the high refractive index fine particles is 2.0 or more, the refractive index of the layer can be effectively increased, and if the refractive index is 3.0 or less, there is no inconvenience such as coloring of the particles. Therefore, it is preferable. Further, if the average particle diameter of the primary particles of the high refractive index fine particles is 100 nm or less, it is preferable because the haze value of the formed fine particle layer is increased and the transparency of the layer is not impaired. It is preferable because a high refractive index is maintained.
Particle diameter of the high refractive index fine particles are expressed as the average primary particle diameter with transmission electron microscope (TEM) photograph. The average primary particle diameter is expressed as an average value of the maximum diameters of the respective fine particles. When the major axis diameter and the minor axis diameter are included, the average value of the major axis diameters of the respective fine particles is defined as the average primary particle diameter.

Examples of the high refractive index fine particles include Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, Y, and other oxides or composite oxides, sulfides. The particle | grains which have as a main component are mentioned. Here, the main component means a component having the largest content (mass%) among the components constituting the particles. More preferable high refractive index fine particles in the present invention are particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn.

The high refractive index fine particles may contain various elements in the particles (hereinafter, such elements may be referred to as containing elements).
Examples of the contained element include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, Bi, P, and S. In the case of tin oxide or indium oxide, it is preferable to contain a contained element such as Sb, Nb, P, B, In, V, or halogen in order to increase the conductivity of the particles, and in particular, antimony oxide is contained in an amount of 5% by mass to 20%. Most preferred is a composition containing 1% by mass.

The high refractive index fine particles are inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from Co, Zr, and Al as contained elements (hereinafter also referred to as “specific oxide”). Is mentioned. Among these, Co is particularly preferable.
The total content of Co, Al, and Zr is preferably 0.05% by mass to 30% by mass with respect to Ti, more preferably 0.1% by mass to 10% by mass, and 0.2% by mass to 7% by mass. More preferably, 0.3% by mass to 5% by mass is particularly preferable, and 0.5% by mass to 3% by mass is most preferable.
The contained elements Co, Al, Zr is present in or on the high refractive index fine particle mainly comprising titanium dioxide. It is more preferable that it exists in the high refractive index fine particle mainly composed of titanium dioxide, and it is more preferable that it exists in both the inside and the surface. Among these contained elements, the metal element may exist as an oxide.

As another preferable high refractive index fine particle, composite oxidation of titanium element and at least one metal element (hereinafter also abbreviated as “Met”) selected from metal elements whose oxide has a refractive index of 1.95 or more. In addition, the composite oxide includes inorganic fine particles doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific multi-oxide”). Can be mentioned. Here, examples of the metal element having a refractive index of the oxide of 1.95 or higher include Ta, Zr, In, Nd, Sb, Sn, and Bi. Among these, Ta, Zr, Sn, and Bi are particularly preferable.
From the viewpoint of maintaining the refractive index, the content of the metal ions doped in the specific composite oxide is within a range not exceeding 25 mass% with respect to the total amount of metal [Ti + Met] constituting the composite oxide. From 0.05% by weight to 10% by weight, more preferably from 0.1% by weight to 5% by weight, and particularly preferably from 0.3% by weight to 3% by weight.

The doped metal ion may exist as a metal ion or in any form of a metal atom, and may appropriately exist from the surface to the inside of the composite oxide. It is preferable to exist both on the surface and inside of the composite oxide.

The high refractive index fine particles preferably have a crystal structure. The crystal structure is preferably composed mainly of rutile, a mixed crystal of rutile / anatase, and anatase, particularly preferably a rutile structure. Accordingly, the high refractive index fine particles of the specific oxide or the specific double oxide have a refractive index of 1.9 to 2.8, which is preferable. The refractive index is more preferably 2.1 to 2.8, still more preferably 2.2 to 2.8. As a result, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the fine particle layer itself and the upper / lower layers in contact with the fine particle layer can be remarkably improved.

A conventionally known method can be used as a method of doping the specific metal element or metal ion described above. For example, methods described in JP-A-5-330825, JP-A-11-263620, JP-A-11-512336, European Patent No. 0335773, etc .; ion implantation methods (for example, Shunichi Gonda, Ishikawa Junzo, Eiji Kamijo, “Ion Beam Applied Technology” CMC Co., Ltd., published in 1989, Yasushi Aoki, “Surface Science” 18 (5), 262, 1998, Shoichi Anbo, “Surface Science” 20 (2), 60 pages, 1999, etc.].

The high refractive index fine particles may be surface treated. The surface treatment is a modification of the surface of the particles using an inorganic compound and / or an organic compound, whereby the wettability of the surface of the high refractive index fine particles is adjusted, and the fine particles are formed in an organic solvent. Dispersibility and dispersion stability in the layer composition are improved. Examples of inorganic compounds adsorbed physicochemically on the particle surface include silicon-containing inorganic compounds (such as SiO ₂ ), aluminum-containing inorganic compounds [Al ₂ O ₃ , Al (OH) _3, etc.], and cobalt. Inorganic compounds containing (CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ etc.), inorganic compounds containing zirconium [ZrO ₂ , Zr (OH) ₄ etc.], inorganic compounds containing iron (Fe ₂ O ₃ etc.) ), Etc.

As the organic compound used for the surface treatment, conventionally known surface modifiers of inorganic fillers such as metal oxides and inorganic pigments can be used. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, published in 2001).

Specifically, an organic compound having a polar group having an affinity for the surface of the high refractive index fine particles, and a coupling compound can be mentioned. Examples of the polar group having affinity with the surface of the high refractive index fine particles include a carboxy group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, an amino group, and the like. Compounds containing seeds are preferred. For example, long chain aliphatic carboxylic acids (eg, stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, etc.), polyol compounds (eg, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ECH (epichlorohydrin) modified glycerol Triacrylate, etc.}, phosphono group-containing compounds {for example, EO (ethylene oxide) modified phosphoric triacrylate, etc.}, alkanolamines {ethylenediamine EO adduct (5 mol), etc.}.

Examples of the coupling compound include conventionally known organometallic compounds, and include silane coupling agents, titanate coupling agents, aluminate coupling agents, and the like. Silane coupling agents are most preferred. Specific examples include compounds described in paragraph numbers [0011] to [0015] of JP-A Nos. 2002-9908 and 2001-310423. Two or more kinds of compounds used for these surface treatments can be used in combination.

The high refractive index fine particles are also preferably fine particles having a core / shell structure in which a shell made of another inorganic compound is formed using the high refractive index fine particles as a core. The shell is preferably an oxide composed of at least one element selected from Al, Si, and Zr. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

The shape of the high refractive index fine particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a rice granular shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape is preferable. The high refractive index fine particles may be used alone or in combination of two or more.
The content of the high refractive index fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably in the range where the refractive index of the polymer can be 1.55 to 1.95.

<< Polymer >>
The polymer is preferably at least one of (A) an organic binder, (B) an organometallic compound containing a hydrolyzable functional group, and a partial condensate of this organometallic compound.

-(A) Organic binder-
As the organic binder (A), (1) a conventionally known thermoplastic resin,
(2) A combination of a conventionally known reactive curable resin and a curing agent, or (3) a combination of a binder precursor (a curable polyfunctional monomer or polyfunctional oligomer described below) and a polymerization initiator. Binders to be used.

It is preferable that a fine particle layer composition containing the organic binder (1), (2) or (3), the fine particles, and the highly refractive fine particles is prepared. This fine particle layer composition is coated on a support to form a coating film, and then cured by a method according to the binder component to form a fine particle layer. The curing method is appropriately selected depending on the type of the binder component. For example, the crosslinking reaction or polymerization reaction of a curable compound (for example, a polyfunctional monomer, a polyfunctional oligomer, etc.) by at least one of heating and light irradiation. The method of raising is mentioned. Especially, the method of forming the binder which hardened | cured the crosslinking reaction or the polymerization reaction of the curable compound by irradiating light using the combination of said (3) is preferable.

Furthermore, it is preferable that the dispersing agent contained in the fine particle dispersion is subjected to a crosslinking reaction or a polymerization reaction simultaneously with or after the coating of the fine particle layer composition.

The binder in the cured film produced in this way is, for example, a curable polyfunctional monomer or polyfunctional oligomer that is a precursor of the dispersant and a precursor of the binder undergoes a crosslinking or polymerization reaction, and the binder has an anion of the dispersant. It becomes a form in which a sex group is incorporated. Furthermore, since the binder in the cured film has a function of maintaining the dispersion state of the high refractive index fine particles, the crosslinked or polymerized structure imparts a film forming ability to the binder and contains the high refractive index fine particles. The physical strength, chemical resistance, and weather resistance in the cured film can be improved.

{Thermoplastic resin (A-1)}
There is no restriction | limiting in particular as a thermoplastic resin of said (1), According to the objective, it can select suitably, For example, a polystyrene resin, a polyester resin, a cellulose resin, a polyether resin, a vinyl chloride resin, a vinyl acetate resin, Examples thereof include vinyl chloride-vinyl acetate copolymer resin, polyacrylic resin, polymethacrylic resin, polyolefin resin, urethane resin, silicone resin, and imide resin.

{Combination of reactive curable resin and curing agent (A-2)}
As the reactive curable resin (2), it is preferable to use a thermosetting resin and / or an ionizing radiation curable resin.
There is no restriction | limiting in particular as said thermosetting resin, According to the objective, it can select suitably, For example, a phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy Examples thereof include resins, amino alkyd resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins, and the like.
The ionizing radiation curable resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a radical polymerizable unsaturated group {(meth) acryloyloxy group, vinyloxy group, styryl group, vinyl group, etc. } And / or a resin having a functional group such as a cationically polymerizable group (epoxy group, thioepoxy group, vinyloxy group, oxetanyl group, etc.), for example, a relatively low molecular weight polyester resin, polyether resin, (meth) acrylic resin, Examples thereof include epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, and polythiol polyene resins.

As needed for these reactive curable resins, a crosslinking agent (for example, an epoxy compound, a polyisocyanate compound, a polyol compound, a polyamine compound, a melamine compound, etc.), a polymerization initiator (for example, an azobis compound, an organic peroxide compound, Conventionally known compounds such as curing agents such as organic halogen compounds, onium salt compounds, and UV photoinitiators such as ketone compounds) and polymerization accelerators (organic metal compounds, acid compounds, basic compounds, etc.) are used. . Specific examples include compounds described by Fuzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” (published by Taiseisha, 1981).

{Combination of binder precursor and polymerization initiator (A-3)}
Hereinafter, a method for forming a cured binder by crosslinking or polymerizing a curable compound by light irradiation using the combination of (3), which is a preferable method for forming a cured binder, will be mainly described.

The functional group of the photocurable polyfunctional monomer or polyfunctional oligomer that is the precursor of the binder may be any of a radical polymerizable functional group and a cationic polymerizable functional group.

Examples of the radical polymerizable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group. Among these, a (meth) acryloyl group is particularly preferable, and a polyfunctional monomer containing two or more radically polymerizable groups in the molecule is particularly preferable.

The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. A compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule is preferable. Such compounds are widely known in the polymer material field, in the present invention, they can be used without any particular limitation. These can have chemical forms such as monomers, prepolymers (ie, dimers, trimers and oligomers) or mixtures thereof, and copolymers thereof.

Examples of the radical polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like. Among these, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are particularly preferable.

Also, addition reaction products of unsaturated carboxylic acid esters and amides having nucleophilic substituents such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates and epoxies, polyfunctional carboxylic acids. A dehydration condensation reaction product with an acid or the like is also preferably used. A reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As yet another example, a compound group in which an unsaturated phosphonic acid, styrene, or the like is substituted for the unsaturated carboxylic acid may be used.

Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like. . Polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, as described in paragraphs [0026] to [0027] of JP-A-2001-139663, for example The compound of this is mentioned.

Other polymerizable esters include, for example, vinyl alcohol, allyl methacrylate, allyl acrylate, aliphatic alcohols described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and the like. Those having an aromatic skeleton described in JP-A-2-226149 and those having an amino group described in JP-A-1-165613 are also preferably used.

Specific examples of polymerizable amides formed from aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and diethylenetriamine tris (meth) acrylamide. And xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B-54-21726.

Furthermore, vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708, etc.), urethane acrylates (Japanese Patent Publication No. 2-16765, etc.), ethylene oxide skeleton Urethane compounds having a characteristic (Japanese Patent Publication No. 62-39418, etc.), polyester acrylates (Japanese Patent Publication No. 52-30490, etc.), and further described in Journal of Japan Adhesion Association Vol. 20, No. 7, pages 300-308 (1984) Photocurable monomers and oligomers can also be used. Two or more kinds of these radical polymerizable polyfunctional monomers may be used in combination.

Next, a cationically polymerizable group-containing compound (hereinafter, also referred to as “cationic polymerizable compound” or “cationic polymerizable organic compound”) that can be used for forming the binder of the fine particle layer will be described.

As the cationic polymerizable compound, any compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used. Examples thereof include a compound, a cyclic thioether compound, a cyclic ether compound, a spiro orthoester compound, a vinyl hydrocarbon compound, and a vinyl ether compound. One or more of the cationically polymerizable organic compounds may be used.

As the cation polymerizable group-containing compound, the number of cation polymerizable groups in one molecule is preferably 2 to 10, more preferably 2 to 5. The average molecular weight of the compound is preferably 3,000 or less, more preferably 200 to 2,000, and still more preferably 400 to 1,500. If the average molecular weight is not less than the lower limit, there will be no inconvenience such as volatilization in the film formation process. If the average molecular weight is not more than the upper limit, the compatibility with the composition for the fine particle layer will not occur. This is preferable because it does not cause problems such as deterioration.

Examples of the epoxy compound include aliphatic epoxy compounds and aromatic epoxy compounds.

Examples of the aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, glycidyl acrylate, homopolymers and copolymers of glycidyl methacrylate, and the like. be able to. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene And so on. Examples of the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or unsaturated alicyclic rings (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc. ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.

Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of monovalent or polyvalent phenols having at least one aromatic nucleus, or alkylene oxide adducts thereof. Examples of these epoxy compounds include compounds described in paragraphs [0084] to [0086] of JP-A No. 11-242101 and paragraphs [0044] to [0046] of JP-A No. 10-158385. And the compounds described.

Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of fast curability. One of the epoxy compounds may be used alone, or two or more may be used in appropriate combination.

The cyclic thioether compound, in place of the epoxy ring of the epoxy compound include compounds having a thioepoxy ring.

Specific examples of the compound containing an oxetanyl group as the cyclic ether compound include compounds described in paragraphs [0024] to [0025] in JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.

Examples of the spiro ortho ester compound include compounds described in JP 2000-506908 A.

Examples of vinyl hydrocarbon compounds include styrene compounds, vinyl group-substituted alicyclic hydrocarbon compounds (vinyl cyclohexane, vinyl bicycloheptene, etc.), compounds described in the above radical polymerizable monomers, propenyl compounds {"J. Polymer Science: Part A: Polymer Chemistry ", vol. 32, page 2895 (1994), etc.}, alkoxy allene compounds {" J. Polymer Science: Part A: Polymer Chemistry ", vol. 33, page 2493 (1995), etc.}, vinyl compounds {"J. Polymer Science: Part A: Polymer Chemistry", 34, 1015 (1996), JP-A-2002-29162, etc.}, isopropenylation Object { "J.Polymer Science: Part A: Polymer Chemistry", 34, pp. 2051 (1996) described the like} and the like can be exemplified. You may use these in combination of 2 or more types as appropriate.

The polyfunctional compound is preferably a compound containing in the molecule at least one selected from the radical polymerizable group and the cationic polymerizable group. Examples thereof include compounds described in paragraph numbers [0031] to [0052] in JP-A-8-277320, compounds described in paragraph number [0015] in JP-A 2000-191737, and the like. The compounds used in the present invention are not limited to these.

The radical polymerizable compound and the cation polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 More preferably, it is contained in a ratio of ˜30: 70.

Next, the polymerization initiator used in combination with the binder precursor in the combination (3) will be described in detail.

Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
The polymerization initiator by light and / or heat radiation is preferably a compound which generates a radical or an acid. The photopolymerization initiator preferably has a maximum absorption wavelength of 400 nm or less. Thus the absorption wavelength in the ultraviolet region, can be implemented to handle under white light. A compound having a maximum absorption wavelength in the near infrared region can also be used.

The compound that generates radicals refers to a compound that generates radicals by irradiation with light and / or heat, and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group. A known polymerization initiator, a compound having a bond having a small bond dissociation energy, and the like can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

Examples of the compound that generates radicals include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, organic peroxide compounds (Japanese Patent Laid-Open No. 2001-139663, etc.), amine compounds ( JP-B-44-20189), metallocene compounds (described in JP-A-5-83588, JP-A-1-304453, etc.), hexaarylbiimidazole compounds (US Pat. No. 3,479,185, etc.) And photo radical polymerization initiators such as disulfone compounds (JP-A-5-239015, JP-A-61-166544, etc.), organic halogenated compounds, carbonyl compounds, and organic boric acid compounds.

Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull. Chem. Soc Japan”, Vol. 42, page 2924 (1969), US Pat. 27830, M.M. P. Hutt, “J. Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970) ”and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring.

Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 (published by Technical Information Association, 1991), paragraph numbers [0015] to [0016] of JP-A-8-134404, Examples thereof include compounds described in paragraph numbers [0029] to [0031] of Kaihei 11-217518. Further, benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, benzoin isobutyl ether, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, benzyldimethyl Examples include ketal and acylphosphine oxide.

Examples of the organic borate compound include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin, “Rad. Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borates described in the above. For example, compounds described in the JP-2002-116539 paragraphs JP [0022] ~ [0027]. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes.

These radical generating compounds may be added alone or in combination of two or more. The addition amount is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and still more preferably 1% by mass to 20% by mass with respect to the total amount of the radical polymerizable monomer. In the range of the addition amount, the temporal stability of the composition for the fine particle layer becomes highly polymerizable without any problem.

Next, a photoacid generator that can be used as a photopolymerization initiator will be described in detail.
Examples of the photoacid generator include known compounds such as photoinitiators for photocationic polymerization, photodecolorants for dyes, photochromic agents, or known photoacid generators used in microresists, and the like. And the like. Examples of the photoacid generator include organic halogenated compounds, disulfone compounds, onium compounds, and the like. Among these, organic halogenated compounds and disulfone compounds are particularly preferable. Specific examples of the organic halogen compound and the disulfone compound are the same as those described for the compound generating the radical.

Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like. For example, paragraph numbers [0058] of JP-A-2002-29162 are listed. ] To [0059], and the like.

As the acid generator, an onium salt is particularly preferably used, and among them, a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound and the like.

Specific examples of the onium salt include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A-9-268205 and paragraph Nos. [0010] to [0010] of JP-A No. 2000-71366. Diaryl iodonium salt or triarylsulfonium salt described in JP-A-2001-288205, sulfonium salt of thiobenzoic acid S-phenyl ester described in JP-A-2001-288205, paragraph of JP-A-2001-133696 Examples thereof include the onium salts described in the numbers [0030] to [0033].

Other examples of the photoacid generator include organic acids / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and photoacids having an o-nitrobenzyl type protecting group. Examples thereof include compounds such as a generator and a compound that generates photosulfonic acid to generate sulfonic acid (such as iminosulfonate).

These acid generators may be used alone or in combination of two or more. The addition amount of the acid generator is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass with respect to the total mass of the total cationically polymerizable monomer. % Is more preferable. The addition amount is preferable in the above range from the viewpoint of stability of the composition for fine particle layer, polymerization reactivity, and the like.

In the fine particle layer composition, the radical polymerization initiator is 0.5% by mass to 10% by mass or the cationic polymerization initiator is 1% by mass to 10% by mass with respect to the total mass of the radical polymerizable compound or the cationic polymerizable compound. %, Preferably 1% to 5% by weight of radical polymerization initiator, or more preferably 2% to 6% by weight of cationic polymerization initiator.

In the fine particle layer composition, when a polymerization reaction is performed by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples of these sensitizers include Michler's ketone, amino acids (for example, glycine), organic amines (for example, butylamine, dibutylamine), and the like.

Also, when the polymerization reaction is carried out by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together. The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength region of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Further, it is preferable that the absorption is in the region of 750 nm to 1,400 nm and the molecular extinction coefficient is 20,000 or more. Further, it is more preferable that there is an absorption valley in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent.

As the near infrared spectral sensitizer, various pigments and dyes known as near infrared absorbing pigments and near infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber. Commercial dyes and literature {for example, “Chemical Industry”, May 1986, pages 45-51 “Near-infrared absorbing dyes”, “Development and market trends of functional dyes in the 1990s”, Chapter 2.3. (1990) CMC, “Special Function Dye” (edited by Ikemori and Pilatani, 1986, issued by CMC Corporation), J. Am. FABIAN, “Chem. Rev.”, Vol. 92, pp. 1197-1226 (1992)}, a catalog published in 1995 by Nippon Sensitive Dye Research Institute, and Exciton Inc. Can be used as well as known dyes described in laser dye catalogs and patents issued in 1989.

(B) An organometallic compound containing a hydrolyzable functional group or a partial condensate of this organometallic compound A coating film by a sol / gel reaction using an organometallic compound containing a hydrolyzable functional group as the matrix It is also preferable to form a cured film after formation.

Examples of the organometallic compound include compounds composed of Si, Ti, Zr, Al, and the like.
Examples of the hydrolyzable functional group include an alkoxy group, an alkoxycarbonyl group, a halogen atom, and a hydroxyl group. Among these, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group or a butoxy group are particularly preferred. A preferred organometallic compound is an organosilicon compound represented by the following general formula (2) or a partial hydrolyzate (partial condensate) thereof. In addition, it is a well-known fact that the organosilicon compound represented by the general formula (2) is easily hydrolyzed and subsequently undergoes a dehydration condensation reaction.

General formula (2): (R ²¹ ) _β -Si (Y ²¹ ) _4-β
In the general formula (2), R ²¹ represents a substituted or unsubstituted aliphatic group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms. Y ²¹ represents a halogen atom (for example, chlorine atom, bromine atom, etc.), OH group, OR ²² group, OCOR ²² group. Here, R ²² represents a substituted or unsubstituted alkyl group. β represents an integer of 0 to 3, preferably 0, 1 or 2, particularly preferably 1. However, when β is 0, Y ²¹ represents an OR ²² group or an OCOR ²² group.

In the general formula (2), the aliphatic group represented by R ²¹ preferably has 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, benzyl). Group, phenethyl group, cyclohexyl group, cyclohexylmethyl, hexenyl group, decenyl group, dodecenyl group, etc.). More preferred are those having 1 to 12 carbon atoms, and particularly preferred are 1 to 8 carbon atoms. The aryl group of R ^21, phenyl, naphthyl, anthranyl and the like, preferably phenyl group.

The substituent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, halogen (eg, fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group ( For example, methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl group (eg phenyl, naphthyl etc.), aromatic heterocyclic group (eg furyl, pyrazolyl, pyridyl etc.), alkoxy group (eg Methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (eg phenoxy etc.), alkylthio group (eg methylthio, ethylthio etc.), arylthio group (eg phenylthio etc.), alkenyl group (eg vinyl, 1 -Propenyl, etc.), alkoxysilyl groups (eg trimethoxysilyl, Ethoxysilyl etc.), acyloxy groups {eg acetoxy, (meth) acryloyl etc.}, alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl groups (eg phenoxycarbonyl etc.), carbamoyl groups (eg Carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (for example, acetylamino, benzoylamino, acrylamino, methacrylamino, etc.) are preferred.

Of these substituents, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group {( (Meth) acryloyl}, a polymerizable acylamino group (for example, acrylamino, methacrylamino, etc.). These substituents may be further substituted.

As described above, R ²² represents a substituted or unsubstituted alkyl group, and the alkyl group is not particularly limited, and examples thereof include the same as the aliphatic group of R ²¹ , and the explanation of the substituent in the alkyl group is R ²¹ .

The content of the compound of the general formula (2) is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and more preferably 30% by mass to 50% by mass of the total solid content of the composition for fine particle layer. More preferred is mass%.

Examples of the compound of the general formula (2) include compounds described in paragraph numbers [0054] to [0056] of JP-A No. 2001-166104.

In the fine particle layer composition, the organic binder preferably has a silanol group. By binder has a silanol group, the physical strength of the particle layer, chemical resistance, weather resistance is further improved, which is preferable. The silanol group, for example, as a binder forming component constituting the fine particle layer composition, a binder precursor (such as a curable polyfunctional monomer or polyfunctional oligomer), a polymerization initiator, a dispersion contained in a fine particle dispersion An organic silicon compound represented by the general formula (2) having a crosslinking or polymerizable functional group is blended with the fine particle layer composition together with the agent, and the fine particle layer composition is applied onto the transparent support. The dispersant, the polyfunctional monomer, the polyfunctional oligomer, and the organosilicon compound represented by the general formula (2) can be introduced into the binder by a crosslinking reaction or a polymerization reaction.

The hydrolysis / condensation reaction for curing the organometallic compound is preferably performed in the presence of a catalyst. Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, trifluoroacetic acid, methanesulfonic acid, and toluenesulfonic acid; sodium hydroxide, potassium hydroxide, ammonia, and the like Inorganic bases; organic bases such as triethylamine and pyridine; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium and tetrabutoxytitanate; metal chelate compounds such as β-diketones or β-ketoesters . Specifically, for example, compounds described in paragraphs [0071] to [0083] in JP-A No. 2000-275403 are exemplified.

The ratio of these catalyst compounds in the composition is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 50% by mass, and more preferably 0.5% by mass to 10 mass% is still more preferable. In addition, it is preferable that reaction conditions are suitably adjusted with the reactivity of an organometallic compound.

In the fine particle layer composition, the matrix preferably has a specific polar group. Examples of the specific polar group include an anionic group, an amino group, and a quaternary ammonium group. Specific examples of the anionic group, amino group, and quaternary ammonium group include the same as those described for the dispersant.

-solvent-
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alcohols, ketones, esters, amides, ethers, ether esters, hydrocarbons, halogenated hydrocarbons And the like. Specifically, alcohol (for example, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.), Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methyl Chloroform, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers For example, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol and the like). These may be used individually by 1 type and may use 2 or more types together. Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are particularly preferable. A coating solvent system mainly comprising a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is also preferably used.
The content of the ketone solvent is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 60% by mass or more of the total solvent contained in the fine particle layer composition.

The matrix having a specific polar group is, for example, a binder precursor having a specific polar group (curable polyfunctional monomer or polyfunctional oligomer having a specific polar group) as a cured film forming component in the composition for a fine particle layer. Etc.) and a polymerization initiator, and at least one of the organosilicon compounds represented by the general formula (2) having a specific polar group and having a crosslinkable or polymerizable functional group, and, if desired, A monofunctional monomer having a specific polar group and a crosslinkable or polymerizable functional group is blended, and the coating composition is applied on a transparent support, and the dispersant, monofunctional monomer, or polyfunctional monomer is applied. It is obtained by crosslinking or polymerizing a polyfunctional oligomer and / or an organosilicon compound represented by the general formula (2).

The monofunctional monomer having the specific polar group is preferable because it can function as a fine particle dispersion aid in the fine particle layer composition. Furthermore, after coating, a dispersing agent, polyfunctional monomer, polyfunctional oligomer and cross-linking reaction or polymerization reaction to form a binder to maintain good and uniform dispersibility of the fine particles in the fine particle layer, physical strength, resistance A fine particle layer excellent in chemical properties and weather resistance can be produced.

The fine particle layer composition is formed on the transparent substrate by, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method, an extrusion coating. It can be prepared by applying by a known thin film forming method such as a method and drying, irradiating with light and / or heat. Preferably, curing by light irradiation is advantageous from rapid curing. Furthermore, it is also preferable to perform heat treatment in the latter half of the photocuring treatment.

The light source for light irradiation may be any ultraviolet light region or near-infrared light source, and ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halide lamps may be used as ultraviolet light sources. Xenon lamps, sunlight, etc. Various available laser light sources having wavelengths of 350 nm to 420 nm may be irradiated in a multi-beam form. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 nm to 1,400 nm may be irradiated in a multi-beam form.

In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas, but in order to shorten the polymerization induction period of the radically polymerizable monomer or sufficiently increase the polymerization rate, etc. It is preferable that the atmosphere has a reduced oxygen concentration. Irradiation intensity of ultraviolet irradiation is ^preferably about 0.1mW / cm 2 ~ 100mW / cm 2, irradiation amount on the coating film surface is ^{100mJ / cm 2 ~ 1,000mJ / cm} 2 is preferred. Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

The average thickness of the fine particle layer is preferably 5 μm to 200 μm, and more preferably 5 μm to 50 μm. When the average thickness is less than 5 μm, there is no sufficient light angle conversion by the fine particle layer, and sufficient light extraction efficiency may not be obtained. When the average thickness exceeds 200 μm, light is scattered too much, and backscattering Light increases, more light returns to the inside of the organic electroluminescent layer, light extraction efficiency decreases, and the thick fine particle layer leads to high cost, and the variation in the thickness of the fine particle layer increases, and the light emitting surface There is a risk that the scattering effect will vary.
The average thickness can be determined, for example, by cutting a part of the fine particle layer and measuring with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Co., Ltd.).

Or the light emitting surface of the fine particle layer is flat, or preferably have a planarizing layer on the light emitting surface of the particulate layer. Thereby, an increase in backscattering can be suppressed even if the density of the fine particles is increased. Moreover, foreign matter adhesion is prevented by flattening. Further, when wound up in a roll shape, the surface (particulate layer side) is flat, so that there is an advantage that even when it is in contact with the back surface (barrier layer), it is not damaged.

Examples of the method for flattening the light emitting surface of the fine particle layer include a method of laminating a material obtained by removing the scattering fine particles from the material used for forming the fine particle layer, and laminating the cured fine particle layer on the fine particle layer. .

The planarizing layer preferably has a composition that does not contain the scattering fine particles in the fine particle layer, and can be formed in the same manner as the fine particle layer.
The thickness of the planarizing layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm to 50 μm. When the thickness of the flattening layer is less than 5 μm, the surface of the protruding original fine particle layer cannot be flattened, and when it exceeds 50 μm, the light extraction ability is reduced due to light absorption of the flattening layer. Sometimes.

-Base material-
The shape, structure, size, material and the like of the substrate are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a flat plate shape, and the like. The structure may be a single layer structure or a laminated structure, and the size may be appropriately selected according to the size of the low refractive index layer transfer sheet.

The material for the base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate, and polyimide resin (PI). Polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene-acrylonitrile copolymer, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is preferable, and polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable from the viewpoint of applicability with a roll.
The surface of the substrate is preferably subjected to a surface activation treatment in order to improve the adhesion between the barrier layer and the fine particle layer provided thereon. Examples of the surface activation treatment include glow discharge treatment and corona discharge treatment.

The base material may be appropriately synthesized or a commercially available product may be used.
There is no restriction | limiting in particular as thickness of the said base material, According to the objective, it can select suitably, 10 micrometers or more are preferable and 50 micrometers or more are more preferable.

The moisture permeability of the organic electroluminescent substrate is preferably 1 × 10 ⁻³ g / m ² / day or less, and more preferably 1 × 10 ⁻⁴ g / m ² / day or less.
The moisture permeability can be measured, for example, by the method described in G. NISATO, PCPBOUTEN, PJSLIKKERVEER et al., SID Conference Record of the International Display Research Conference, pages 1435-1438 (measurement method using calcium).
The oxygen permeability of an organic light emitting substrate is preferably not more than ^1cc / m 2 / day, more preferably not more than 0.1cc ^/ m 2 ^/ day.
The oxygen permeability can be measured by, for example, an oxygen permeability measuring device (manufactured by MOCON, MOCON oxygen permeability measuring device, OX-TRAN 1 / 50A).

The organic electroluminescence substrate of the present invention can suppress spectrum modulation due to interference of the barrier layer, surface position dependency of chromaticity, and angle dependency of chromaticity, and can improve light extraction efficiency. Although it can be used for an electroluminescent device or the like, it is particularly preferably used for the organic electroluminescent device of the present invention described below.

(Organic electroluminescent device)
The organic electroluminescent device of the present invention includes at least the organic electroluminescent substrate of the present invention, and includes an organic electroluminescent layer and, if necessary, other members.

-Organic electroluminescent layer-
The organic electroluminescent layer has a pair of electrodes, that is, an anode and a cathode, and a light emitting layer between both electrodes. Examples of the functional layer other than the light emitting layer that can be disposed between both electrodes include a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer.

The organic electroluminescent layer preferably has a hole transport layer between the anode and the light emitting layer, and preferably has an electron transport layer between the cathode and the light emitting layer. Furthermore, a hole injection layer may be provided between the hole transport layer and the anode, or an electron injection layer may be provided between the electron transport layer and the cathode.
In addition, a hole transporting intermediate layer (electron blocking layer) may be provided between the light emitting layer and the hole transporting layer, and an electron transporting intermediate layer (hole blocking layer) is provided between the light emitting layer and the electron transporting layer. Layer) may be provided. Each functional layer may be divided into a plurality of secondary layers.

These functional layers including the light emitting layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a wet coating method, a transfer method, a printing method, and an ink jet method.

--Light emitting layer--
The light-emitting layer receives holes from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, receives electrons from a cathode, an electron injection layer, or an electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light.
The light emitting layer includes a light emitting material. The light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material (in the latter case, the light emitting material may be referred to as a “light emitting dopant” or “dopant”). The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and two or more kinds may be mixed. The host material is preferably a charge transport material. The host material may be one type or two or more types. Furthermore, the light emitting layer may contain a material that does not have charge transporting properties and does not emit light.

The thickness of the light emitting layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 nm to 500 nm, more preferably 3 nm to 200 nm, and further preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. . Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

--- Luminescent material ---
As the light emitting material, a phosphorescent light emitting material, a fluorescent light emitting material, or the like can be preferably used. The luminescent dopant in the present invention has an ionization potential difference (ΔIp) and an electron affinity difference (ΔEa) of 1.2 eV>ΔIp> 0.2 eV and / or 1.2 eV> with respect to the host compound. it is △ Ea> 0.2 eV dopants satisfying the relationship is preferable in view of driving durability.
The light-emitting dopant in the light-emitting layer is contained in the light-emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass generally forming the light-emitting layer. 1% to is preferably contained 50 wt% in view, it is more preferably contained 2 wt% to 50 wt%.

<Phosphorescent material>
In general, examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
The transition metal atom is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum. , more preferably, rhenium, iridium, and platinum, more preferably iridium or platinum.

Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, Inc. 1987, H. Listed by Yersin, "Photochemistry and Photophysics of Coordination Compounds", published by Springer-Verlag, 1987, Akio Yamamoto, "Organic Metal Chemistry-Fundamentals and Applications," published by Yukabosha, 1982, etc. .

The complex may have one transition metal atom in the compound or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

Among these, as phosphorescent materials, for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, WO2004 / 108857A1, WO2005 / 042444A2, WO2005 / 042550A1, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-1235076, JP2003-123982, JP2002-170684, EP121257, JP2002-226495, JP2002 234894, JP 2001-247659, JP 2001-298470, JP 2002-173675, JP 2002-203678, JP 2002-203679, JP 2004-357791, JP 2006-93542, JP 2006-261623, Examples include phosphorescent compounds described in JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, and the like. Among these, Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex are preferable, and Ir complex , Pt complex, or Re complex is more preferable, and Ir complex, Pt complex, or Re complex including at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, metal-sulfur bond is further included. In view of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or an Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

Specific examples of the phosphorescent material include the following compounds, but are not limited thereto.

<Fluorescent material>
The fluorescent material is not particularly limited and can be appropriately selected according to the purpose. For example, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, Coumarin, pyran, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene, styrylamine, aromatic dimethylidin compound, condensed polycyclic aromatic compound (anthracene) , Phenanthroline, pyrene, perylene, rubrene, or pentacene), metal complexes of 8-quinolinol, pyromethene complexes, various metal complexes represented by rare earth complexes, polythiol Emissions, polyphenylene, polymeric compounds such as polyphenylene vinylene, organic silane, or their derivatives can be mentioned.

---- Host material ---
As the host material, a hole-transporting host material having excellent hole-transporting property (may be described as a hole-transporting host) and an electron-transporting host compound having excellent electron-transporting property (described as an electron-transporting host) May be used).

<Hole-transporting host material>
Examples of the hole transporting host material include the following materials. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone Hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, Examples thereof include conductive polymer oligomers such as polythiophene, organic silanes, carbon films, or derivatives thereof.
Among these, indole derivatives, carbazole derivatives, aromatic tertiary amine compounds, thiophene derivatives, and those having a carbazole group in the molecule are preferred, and compounds having a t-butyl substituted carbazole group are more preferred.

<Electron transporting host material>
Examples of the electron transporting host material include pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazol, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, Carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanines, or derivatives thereof (may form condensed rings with other rings), Examples thereof include metal complexes of 8-quinolinol derivatives, various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole, and benzothiazol as ligands. Among these, a metal complex compound is preferable from the viewpoint of durability, and a metal complex having a ligand having at least one nitrogen atom, oxygen atom, or sulfur atom coordinated to a metal is more preferable. Examples of the metal complex electron transporting host include Japanese Patent Application Laid-Open No. 2002-235076, Japanese Patent Application Laid-Open No. 2004-214179, Japanese Patent Application Laid-Open No. 2004-221106, Japanese Patent Application Laid-Open No. 2004-221665, and Japanese Patent Application Laid-Open No. 2004-221068. And compounds described in JP-A-2004-327313.

Specific examples of the hole transporting host material and the electron transporting host material include the following compounds, but are not limited thereto.

--- Hole injection layer, hole transport layer--
The hole injection layer or the hole transport layer is a layer having a function of receiving holes from the anode or the layer on the anode side and transporting them to the cathode side. The hole injecting material and hole transporting material used for these layers may be a low molecular compound or a high molecular compound. Specifically, pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, etc. It is preferable that it is a layer containing.

The hole injection layer or the hole transport layer may contain an electron accepting dopant. As the electron-accepting dopant introduced into the hole injection layer or the hole transport layer, an inorganic compound or an organic compound can be used as long as it has an electron accepting property and oxidizes an organic compound.
Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide. In the case of an organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
These electron-accepting dopants may be used alone or in combination of two or more. The amount of the electron-accepting dopant used varies depending on the type of material, but is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 20% by mass with respect to the hole transport layer material. 1% by mass to 10% by mass is particularly preferable.

The hole injection layer or 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. Also good.

--- Electron injection layer, electron transport layer--
The electron injection layer or the electron transport layer is a layer having a function of receiving electrons from the cathode or a layer on the cathode side and transporting them to the anode side. Electron injection material used in these layers, an electron transport material may be a polymer compound may be a low molecular compound.
Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone Derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic ring tetracarboxylic acid anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, Various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole and benzothiazole as ligands, and organosilane derivatives represented by silole Body, or the like is preferably a layer containing.

The electron injection layer or the electron transport layer may contain an electron donating dopant. The electron-donating dopant introduced into the electron-injecting layer or the electron-transporting layer is not limited as long as it has an electron-donating property and has a property of reducing an organic compound. Alkali metals such as Li and alkaline earths such as Mg Metals, transition metals including rare earth metals, reducing organic compounds, and the like are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
These electron donating dopants may be used alone or in combination of two or more. The amount of the electron-donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, more preferably 1.0% by mass to 80% by mass with respect to the electron transport layer material. 0% by mass to 70% by mass is particularly preferable.

The electron injection layer or the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.

--- Hole blocking layer, electron blocking layer--
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, and is usually provided as an organic compound layer adjacent to the light emitting layer on the cathode side. .
On the other hand, the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing to the anode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the anode side. .
Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. As an example of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be used.
The thickness of the hole blocking layer and the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the hole blocking layer and the electron 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. .

--electrode--
The organic electroluminescent element includes a pair of electrodes, that is, an anode and a cathode. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
Usually, the anode only needs to have a function as an electrode for supplying holes to the organic compound layer, and the cathode only needs to have a function as an electrode for injecting electrons into the organic compound layer. The shape, structure, size, and the like are not particularly limited, and can be appropriately selected from known electrode materials according to the use and purpose of the light-emitting element. As a material which comprises an electrode, a metal, an alloy, a metal oxide, an electroconductive compound, or a mixture thereof etc. are mentioned suitably, for example.

The electrode is not particularly limited and may be appropriately selected depending on the purpose. It is preferable that the anode and the cathode constitute the reflective metal and the translucent metal as the translucent member.

Specific examples of the material constituting the anode include, for example, antimony, fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), zinc oxide indium (IZO). ) Conductive metal oxides, metals such as gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, Examples thereof include organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

Examples of the material constituting the cathode include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium. alloy, a lithium - aluminum alloy, a magnesium - silver alloy, indium, and rare earth metals such as ytterbium. 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 these, an alkali metal and an alkaline earth metal are preferable from the viewpoint of electron injection properties, 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% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).

The method for forming the electrode is not particularly limited, and can be performed according to a known method. For example, a material constituting the electrode from a wet method such as a printing method, 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. In consideration of the suitability, the film can be formed on the substrate according to an appropriately selected method. For example, when ITO is selected as the anode material, it can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like. When a metal or the like is selected as the cathode material, one or more of them can be formed simultaneously or sequentially according to a sputtering method or the like.

In addition, when patterning is performed when forming the electrode, it may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition with a mask overlapped. It may be performed by sputtering or the like, or may be performed by a lift-off method or a printing method.

When a layer having a diffusing effect such as a fine particle layer is provided on a substrate as in the organic electroluminescent device of the present invention, the front chromaticity changes greatly. This is because light of all angles (chromaticity varies depending on the angle dependency) gathers due to the diffusion effect. Basically it moves from red to blue (in the direction of increasing color temperature). Therefore, it is preferable to set the color temperature slightly lower. For example, if the aim is (0.31, 0.31) (white) in the (x, y) chromaticity notation of the CIE color system, the chromaticity of the organic electroluminescent device alone is (0.34, 0. 33) If the chromaticity x and chromaticity y in the vicinity are set to higher values, and designed and manufactured, it is predicted that they will come near the target (0.31, 0.31) with the fine particle layer attached. .
Therefore, the chromaticity of the organic electroluminescence substrate before the fine particle layer is provided is 0.01 to 0.05, and the chromaticity y is 0.01 to 0.05 from the target chromaticity in the CIE color system. It is preferable to set it to be higher by 0.05.

Here, FIG. 1 is a schematic view showing an example of the organic electroluminescent device of the present invention. The organic electroluminescent device of FIG. 1 includes an organic electroluminescent substrate having a barrier layer 3 on the surface of the base material 1 on the organic electroluminescent layer side and a fine particle layer 2 on the light output surface side of the base material 1. Have
An electrode (ITO) 4, an organic layer 5, and an electrode 6 are provided on the barrier layer 3 of the organic electroluminescence substrate, and these are sealed with a sealing can 7.

The organic electroluminescent device can be configured as a device capable of displaying in full color.
As a method for making the organic electroluminescent device of the full color type, for example, as described in “Monthly Display”, September 2000, pages 33-37, the three primary colors (blue (B) , Green color (G), red color (R), each of which emits light corresponding to a three-color light emission method in which a layer structure for emitting light corresponding to green (G) and red (R)) is arranged on a substrate. A white method, a color conversion method for converting blue light emission by a blue light emission layer structure into red (R) and green (G) through a fluorescent dye layer, and the like are known.
In this case, it is preferable to appropriately adjust the laser power and thickness for each pixel of blue (B), green (G), and red (R).
In addition, by using a combination of a plurality of layer structures of different emission colors obtained by the above method, a planar light source having a desired emission color can be obtained. For example, a white light-emitting light source combining blue and yellow light-emitting elements, a white light-emitting light source combining blue (B), green (G), and red (R) organic electroluminescent elements.

The organic electroluminescent device is, for example, a lighting device, a computer, an on-vehicle display, an outdoor display, a home device, a business device, a home appliance, a traffic display, a clock display, a calendar display, a luminescence. It can be suitably used in various fields including cent screens, audio equipment and the like.

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

(Preparation Example 1)
<Method for preparing mixed coating solution 1>
179 parts by weight of distilled water, 46 parts by weight of a surfactant (manufactured by Sanyo Chemical Industries, Ltd., trade name: NAROACTY CL-95), nano-sized fine particles (manufactured by Nissan Chemical Co., Ltd., Snowtex ZL, solid content of 40% by weight) ) 114 parts by mass, fine particles having an average particle diameter of 2 μm (manufactured by Nissan Chemical Co., Ltd., Optobead 2000M, solid content: 100% by mass), 275 parts by mass, aqueous polyurethane (manufactured by Mitsui Chemicals, Takelac series W-6010, solid content) 33 parts by mass) 359 parts by mass and 27 parts by mass of a curing agent (Nisshinbo Co., Ltd., V-02-L2, solid content 40% by mass) are mixed and stirred using a stirrer to prepare mixed coating solution 1 did.

(Preparation Example 2)
<Preparation of mixed coating solution 2>
59 parts by mass of a surfactant (manufactured by Sanyo Chemical Industries, Ltd., trade name: NAROACTY CL-95), 992 parts by mass of aqueous polyurethane (manufactured by Mitsui Chemicals, Takelac series W-6010, solid content 33% by mass), Then, 59 parts by mass of a curing agent (Nisshinbo Co., Ltd., V-02-L2, solid content: 40% by mass) was mixed to prepare a mixed coating solution 2.

Example 1
-Fabrication of organic electroluminescence substrate-
A barrier layer having a barrier property against water and oxygen by forming Al ₂ O ₃ on one surface of a polyethylene terephthalate (PET) film having a thickness of 0.1 mm by vacuum sputtering so that the average thickness is 50 nm. An attached film substrate was produced.
The mixed coating solution 1 was applied to the other surface of the PET film with a wire bar, and was cured by heating at 130 ° C. for 2 minutes. The mixed coating solution 1 was applied thereon, and again heat-cured at 130 ° C. for 2 minutes to prepare a fine particle layer having a thickness of 15 μm.
Thus, an organic electroluminescence substrate of Example 1 was produced.

When the thickness unevenness of the barrier layer was measured for the produced organic electroluminescence substrate as follows, the average thickness was ± 7 nm, and the thickness unevenness was 14 nm.
<Measurement of uneven thickness of barrier layer>
The thickness unevenness of the barrier layer was measured with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Corporation). In addition, the value of thickness unevenness was shown by the average value of nine places measurement.

-Fabrication of organic electroluminescence device-
First, an ITO (Indium Tin Oxide) film was formed on the barrier layer of the organic electroluminescence substrate of Example 1 to a thickness of 100 nm by sputtering.
Next, on the ITO, 4,4 ′, 4 ″ -tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2-TNATA) represented by the following structural formula has the following structure: A hole injection layer doped with 0.3% by mass of F4-TCNQ represented by the formula was co-evaporated to a thickness of 150 nm.

Next, α-NPD (Bis [N- (1-naphthyl) -N-phenyl] benzidine)) is formed on the hole injection layer as a hole transport layer by vacuum deposition so as to have a thickness of 7 nm. did.
Next, an organic material A represented by the following structural formula was vacuum-deposited on the hole transport layer to form a second hole transport layer having a thickness of 3 nm.

Next, an organic material B represented by the following structural formula as a host material on the second hole transport layer, and a phosphorescent light emitting material of 40 mass% with respect to the organic material B is represented by the following structural formula. The light emitting layer doped with the light emitting material A was vacuum evaporated to a thickness of 30 nm.

Next, BAlq (Bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolate) -aluminum (III)) represented by the following structural formula is formed on the white light-emitting layer as an electron transporting layer with a thickness of 39 nm. Vacuum deposition was performed so that

Next, on the electron transport layer, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) represented by the following structural formula is used as an electron injection layer so that the thickness is 1 nm. did.

Next, LiF was deposited as a buffer layer on the electron injection layer to a thickness of 1 nm, and aluminum was deposited thereon as an electrode layer to a thickness of 100 nm.
The produced laminated body is moved from a vacuum to a room under a nitrogen atmosphere and sealed with a sealing can. A hygroscopic material was previously pasted inside the sealing can. Thus, the organic electroluminescent device of Example 1 shown in FIG. 1 was produced.

(Example 2)
-Fabrication of organic electroluminescence substrate-
On one surface of a polyethylene terephthalate (PET) film having a thickness of 100 μm, a composition comprising a polymerizable compound shown in Table 1 below (total 20 parts by mass) and a polymerization initiator (Lamberti, Ezacure KTO46). A film was prepared by using methyl ethyl ketone so as to have a dry average thickness of 1,000 nm, and cured by irradiation with an ultraviolet ray irradiation amount of 1.2 J / cm ² in an oxygen 100 ppm atmosphere to prepare an organic layer.
An inorganic layer (Al ₂ O ₃ ) was formed on the organic layer by sputtering so that the average thickness was 50 nm, and a film substrate with a barrier layer having a barrier property against water and oxygen was produced.

Next, the mixed coating solution 1 was applied to the other surface of the PET film with a wire bar and cured by heating at 130 ° C. for 2 minutes. The mixed coating solution 1 was applied thereon and cured by heating at 130 ° C. for 2 minutes to prepare a fine particle layer having a thickness of 15 μm.
Thus, an organic electroluminescent substrate of Example 2 was produced.
For the produced organic electroluminescent substrate, the thickness unevenness of the barrier layer was measured in the same manner as in Example 1. As a result, the inorganic layer had an average thickness of ± 7 nm, the thickness unevenness of 14 nm was generated, and the organic layer had an average thickness of ± The thickness was 20 nm, and the thickness unevenness of 40 nm was generated. As a whole barrier layer, the thickness unevenness of 42 nm was generated.

-Fabrication of organic electroluminescence device-
Next, an organic electroluminescent layer is formed on the barrier layer of the organic electroluminescent substrate of Example 2 produced in the same manner as in Example 1 to produce the organic electroluminescent device of Example 2 shown in FIG. did.

(Example 3)
-Fabrication of organic electroluminescence substrate-
On one surface of a polyethylene terephthalate (PET) film having a thickness of 0.1 mm, in the same manner as in Example 2, an organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic Nine layers were formed in the order of the layers by a coating method and a sputtering method, a barrier layer was formed, and a film substrate with a barrier layer having a barrier property against water and oxygen was produced.
The mixed coating solution 1 was applied to the other surface of the PET film with a wire bar, and was cured by heating at 130 ° C. for 2 minutes. The mixed coating solution 1 was applied thereon and cured by heating at 130 ° C. for 2 minutes to prepare a fine particle layer having a thickness of 15 μm.
Thus, an organic electroluminescence substrate of Example 3 was produced.
About the produced organic electroluminescent board | substrate, when the thickness nonuniformity of the barrier layer was measured like Example 1, the thickness nonuniformity of 94 nm had arisen as the whole barrier layer.

-Fabrication of organic electroluminescence device-
An organic electroluminescence layer was formed on the barrier layer of the produced organic electroluminescence substrate of Example 3 in the same manner as in Example 1 to produce the organic electroluminescence device of Example 3 shown in FIG.

(Example 4)
-Fabrication of organic electroluminescence substrate-
On one surface of a polyethylene terephthalate (PET) film having a thickness of 0.1 mm, in the same manner as in Example 2, an organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic layer / inorganic layer / organic Nine layers were formed in the order of the layers by a coating method and a sputtering method, a barrier layer was formed, and a film substrate with a barrier layer having a barrier property against water and oxygen was produced.
The mixed coating solution 1 was applied to the other surface of the PET film with a wire bar, and was cured by heating at 130 ° C. for 2 minutes. The mixed coating solution 1 was applied thereon and cured by heating at 130 ° C. for 2 minutes to form a fine particle layer having a thickness of 15 μm.
Further, the mixed coating solution 2 was coated on the fine particle layer with a wire bar, and cured by heating at 130 ° C. for 2 minutes. The mixed coating solution 2 was applied thereon and cured by heating at 130 ° C. for 2 minutes to form a planarization layer having a thickness of 12.5 μm.
About the produced organic electroluminescent board | substrate, when the thickness nonuniformity of the barrier layer was measured like Example 1, the thickness nonuniformity of 101 nm had arisen as the whole barrier layer.

-Fabrication of organic electroluminescence device-
Next, an organic electroluminescent layer is formed on the barrier layer of the produced organic electroluminescent substrate of Example 4 in the same manner as in Example 1 to produce the organic electroluminescent device of Example 4 shown in FIG. did.

(Comparative Example 1)
-Fabrication of organic electroluminescence device-
In Example 1, it replaced with the organic electroluminescent board | substrate produced in Example 1, and it carried out similarly to Example 1 except having used the glass substrate (The Corning company make, glass substrate Eagle XG (thickness 0.7mm)). The organic electroluminescent device of Comparative Example 1 shown in FIG. 5 was produced.

(Comparative Example 2)
-Fabrication of organic electroluminescent substrate and organic electroluminescent device-
In the production of the organic electroluminescence substrate in Example 1, the organic electroluminescence substrate of Comparative Example 2 was produced in the same manner as in Example 1 except that the fine particle layer was not formed.
About the produced organic electroluminescent board | substrate, when the thickness nonuniformity of the barrier layer was measured like Example 1, the thickness nonuniformity of 15 nm had arisen.
Next, in Example 1, Comparative Example 2 shown in FIG. 6 was performed in the same manner as Example 1 except that the organic electroluminescent substrate of Comparative Example 2 was used instead of the organic electroluminescent substrate of Example 1. An organic electroluminescent device was prepared.

(Comparative Example 3)
-Fabrication of organic electroluminescent substrate and organic electroluminescent device-
In the production of the organic electroluminescence substrate in Example 2, the organic electroluminescence substrate of Comparative Example 3 was produced in the same manner as in Example 2 except that the fine particle layer was not formed.
About the produced organic electroluminescent board | substrate, when the thickness nonuniformity of the barrier layer was measured like Example 1, the thickness nonuniformity of 41 nm had arisen as the whole barrier layer.
In Example 2, the organic electroluminescence substrate of Comparative Example 3 shown in FIG. 7 was used in the same manner as in Example 2 except that the organic electroluminescence substrate of Comparative Example 3 was used instead of the organic electroluminescence substrate of Example 2. A light emitting device was manufactured.

(Comparative Example 4)
-Fabrication of organic electroluminescent substrate and organic electroluminescent device-
In the production of the organic electroluminescence substrate of Example 3, an organic electroluminescence substrate of Comparative Example 4 was produced in the same manner as in Example 3 except that the fine particle layer was not formed.
When the thickness of the barrier layer was measured for the produced organic electroluminescent substrate in the same manner as in Example 1, the thickness of the entire barrier layer was found to be 98 nm.
In Example 3, the organic electroluminescence substrate of Comparative Example 4 shown in FIG. 8 was used in the same manner as in Example 3 except that the organic electroluminescence substrate of Comparative Example 4 was used instead of the organic electroluminescence substrate of Example 3. A light emitting device was manufactured.

(Comparative Example 5)
<Production of organic electroluminescent device>
9 is used in the same manner as in Example 3 except that a substrate having a barrier layer and a concavo-convex layer formed thereon is used instead of the organic electroluminescence substrate of Example 3. An electroluminescent device was produced.
About the produced organic electroluminescent board | substrate, when the thickness nonuniformity of the barrier layer was measured like Example 1, the thickness nonuniformity of 95 nm was produced as the whole barrier layer.
-Fabrication of substrate with uneven layer-
In the same manner as in Example 3, nine barrier layers were formed on one surface of the base material using a polyethersulfone film (thickness: 100 μm) as a base material.
On the other surface of the substrate, 13 parts by mass of bis (4-methacryloylthio-3,5-phenyl) sulfide (manufactured by Sumitomo Seika Co., Ltd., MPSMA), epoxy acrylate (manufactured by Showa Polymer Co., Ltd., VR-60) -LAV) A uniform mixed coating solution consisting of 6 parts by mass, 54 parts by mass of diethylene glycol, 26 parts by mass of ethyl acetate, and 1 part by mass of photoinitiator (manufactured by Ciba Specialty Chemicals, IRGACURE907) was applied at 120 ° C. After heating and drying for 10 minutes, a PET film for stamping foil (Lumirror X44, manufactured by Toray Industries, Inc.) was bonded and cured by UV irradiation.
The PET film was peeled from the substrate to form a concavo-convex layer having a thickness of 2 μm (refractive index (n _D ) of the concavo-convex layer 1.65, average roughness 260 nm).

Next, with respect to the organic electroluminescence devices of Examples 1 to 4 and Comparative Examples 1 to 5, the chromaticity due to the dependence of the front luminance and chromaticity on the light distribution angle and the machine difference (substrate surface position difference) is as follows. Variation, moisture permeability, and oxygen permeability were measured. The results are shown in Table 2.

<Measurement of light distribution angle dependency of front luminance and chromaticity>
Using a source measure unit type 2400 manufactured by Toyo Technica Co., Ltd., a constant DC voltage was applied to each organic electroluminescent device to emit light. The front luminance was measured by using a spectral radiance meter (SR-3, manufactured by Topcon) at a current value of 10 mA / cm ^{2 at} the center of the light emitting surface.
For the light distribution during substrate rotation, a spectral luminance meter (CS-2000, manufactured by Konica Minolta Co., Ltd.) was used to measure the light distribution and spectrum during light distribution measurement. In addition, the rotation stage which sets an organic electroluminescent apparatus at the time of light distribution measurement used the handmade thing which rotates automatically. A constant current amount (10 mA / cm ² ) is passed through the substrate to emit light, while the direction perpendicular to the substrate (light emitting surface) is set to 0 °, and the range of ± 80 ° is set to the spectroluminometer in 5 ° steps. The light intensity distribution and spectrum were measured. Using the CIE color system, the chromaticity x value and y value at 0 ° and 80 ° are calculated from the obtained spectrum, and the amount of change in chromaticity x value and y value from 0 ° to 80 ° (Δx, Δy) was determined.

<Chromaticity variation due to machine difference (substrate surface position difference)>
Since the barrier layer has uneven thickness in the substrate surface, the thickness of the barrier layer varies depending on the cut-out position of the substrate with the barrier layer. For this reason, there is a possibility that the organic electroluminescence device has different chromaticity (variation in machine difference) due to machine difference (positional difference on the substrate surface). Then, as shown in FIG. 17, the board | substrate with a barrier layer was cut, several samples (for example, A, B, C, D in FIG. 17) were produced, and the difference in machine difference was measured. The measurement was performed in the same manner as the front luminance measurement. Using the CIE color system from the obtained spectrum of each organic electroluminescent device, the respective chromaticity x value and y value are calculated, and values Δx ′ and Δy that maximize the difference between the chromaticity x value and the y value are obtained. '(The maximum machine difference chromaticity) was calculated.

<Measurement of moisture permeability>
G.NISATO, PCPBOUTEN, PJSLIKKERVEER et al., SID Conference Record of the International Display Research Conference (Measurement method using calcium) described on pages 1435-1438, temperature was measured at 40 ° C. and relative humidity was 90%. .
In this measurement method, when the water permeability is 1.0 × 10 ⁻⁵ g / m ² / day or less, there is a possibility of a problem in numerical accuracy. Therefore, <1.0 × 10 ⁻⁵ is described.

<Measurement of oxygen permeability>
The measurement was performed using an oxygen permeability measuring device (MOCON oxygen permeability measuring device OX-TRAN 1 / 50A manufactured by MOCON).
In this measurement method, the oxygen permeability is 0.1 cc / m ² / day, which is the measurement limit.

<Shape change of emission spectrum by providing a barrier layer, uneven relief layer, or fine particle layer>
12 to 15 show the emission spectra of the organic electroluminescent devices of Comparative Example 1, Comparative Example 4, Comparative Example 5, and Example 4. FIG. Similarly to the measurement of the front luminance, the emission spectrum is 10 mA / cm at the center of the light emitting surface by using a source measure unit 2400 manufactured by Toyo Technica Co., Ltd. and applying a DC constant voltage to each organic electroluminescent device. The current was measured with a spectral radiance meter (SR-3, manufactured by Topcon) at a current value of ² .
From these results, the emission spectrum modulated by the barrier layer (Comparative Example 1 → Comparative Example 4) is relaxed by the uneven relief layer (Comparative Example 4 → Comparative Example 5). It was observed that it was removed (Comparative Example 5 → Example 4).
In addition, FIG. 16 shows emission spectra in Comparative Example 4-1 and Comparative Example 4-2, which are organic electroluminescent devices having the same configuration as Comparative Example 4 and simultaneously manufactured and having a barrier layer. From the results of FIG. 16, the emission spectrum shape of the organic electroluminescence device with a barrier layer of Comparative Example 4 is the same as in Comparative Example 4-1 and Comparative Example 4-2. In spite of this, it was recognized that the shape of the emission spectrum was changed due to the uneven thickness of the barrier layer, and the chromaticity was caused to vary by machine difference (maximum machine difference chromaticity).

From the results of Table 2, the organic electroluminescent device of Example 1 has a front luminance of 2,360 cd / m ² at a current value of 10 mA / cm ^{2 at} the center of the light emitting surface, and the organic of Comparative Example 2 without a fine particle layer. It was found that the luminance was increased by about 50% compared to the electroluminescent device. Further, the change in chromaticity (Δx, Δy) during rotation of the substrate in Example 1 was much smaller than that in Comparative Example 2. Further, the maximum machine-difference chromaticity (Δx ′, Δy ′), which is the distribution of chromaticity in the substrate surface, is smaller than that of Comparative Example 2, and the chromaticity difference due to the uneven thickness of the barrier layer is suppressed.
The organic electroluminescent device of Example 2 has a luminance value of 2,365 cd / m ² at a current value of 10 mA / cm ^{2 at} the center of the light emitting surface, and compared with the organic electroluminescent device of Comparative Example 3 having no fine particle layer. It was found that the luminance increased by about 50%. Further, the change in chromaticity (Δx, Δy) during rotation of the substrate in Example 2 was much smaller than that in Comparative Example 3. Further, the maximum machine-difference chromaticity (Δx ′, Δy ′), which is the distribution of chromaticity in the substrate surface, is smaller than that of Comparative Example 3, and the chromaticity difference due to the uneven thickness of the barrier layer is suppressed.
The organic electroluminescent device of Example 3 has a luminance value of 2,362 cd / m ² at a current value of 10 mA / cm ^{2 at} the center of the light emitting surface, and has no fine particle layer, as compared with the organic electroluminescent device of Comparative Example 4. It was found that the luminance increased by about 50%. In addition, the change in chromaticity (Δx, Δy) during rotation of the substrate in Example 3 was much smaller than that in Comparative Example 4. Further, the maximum machine-difference chromaticity (Δx ′, Δy ′), which is the distribution of chromaticity in the substrate surface, is smaller than that of Comparative Example 4, and the chromaticity difference due to the uneven thickness of the barrier layer is suppressed.
The organic electroluminescent device of Example 4 has a front luminance of 2,722 cd / m ² at a current value of 10 mA / cm ^{2 at} the center of the light emitting surface, and is smaller than the organic electroluminescent device of Comparative Example 4 having no fine particle layer. About 70% of the brightness increased. In addition, the change in chromaticity (Δx, Δy) during substrate rotation was much smaller than that in Comparative Example 4. Further, the maximum machine-difference chromaticity (Δx ′, Δy ′), which is the distribution of chromaticity in the substrate surface, is smaller than that of Comparative Example 4, and the chromaticity difference due to the uneven thickness of the barrier layer is suppressed.
The organic electroluminescence devices of Comparative Examples 2 to 4 have substantially the same luminance at the same current value as that of Comparative Example 1, but Comparative Examples 2 to 4 have a large chromaticity angle dependency of the light distribution. The maximum machine-difference chromaticity (Δx ′, Δy ′) that is the in-plane distribution of the substrate is also larger than that of Comparative Example 1. Presumed to be the influence of interference and unevenness of the barrier layer, which was not found in the glass substrate.
In comparison with Comparative Example 4, the organic electroluminescent device of Comparative Example 5 has a luminance of 1,884 cd / m ² at the same current value, and the extraction efficiency is slightly lower than 20%. The result is inferior. Further, the chromaticity angle dependency (Δx, Δy) of light distribution and the maximum machine difference chromaticity (Δx ′, Δy ′) are also smaller than those of the comparative example 4, but compared to the examples 3 and 4. The effect of suppressing the chromaticity angle dependency of light distribution and the maximum machine difference chromaticity is small.

(Application 1)
-Fabrication of flexible organic electroluminescent panel-
In the production of the organic electroluminescent device in Example 4, the laminated body after aluminum deposition was transferred to a CVD device, and a SiN film as the inorganic sealing layer 11 was formed to a thickness of 3 μm. After the film formation, the laminate was transferred to a glove box under a nitrogen atmosphere, the solid adhesive layer 12 was attached onto the SiN film, thermocompression bonded, and a PET film 13 having a thickness of 100 μm was attached onto the solid adhesive layer 12. The solid adhesive layer was cured by heating to produce a flexible organic electroluminescent panel shown in FIG.

(Application example 2)
-Fabrication of flexible organic electroluminescent panel-
In the production of the organic electroluminescent device in Example 4, the laminated body after aluminum deposition was transferred to a glove box under a nitrogen atmosphere, and a filler 16 was applied to the center of the laminated body near the electrode, and a sealing material 15 was applied around the substrate. Further thereon, a PET film (no fine particle layer) 13 with a barrier layer 14 in which a total of nine organic layers and inorganic layers same as those of the substrate produced in Example 4 were laminated, and the barrier layer side with a filler 16 And pasted toward the application side of the sealing material 15. The flexible organic electroluminescent panel shown in FIG. 11 was produced by solidifying the filler 16 and the sealing material 15 by UV irradiation and heating.

The organic electroluminescent substrate and the organic electroluminescent device of the present invention are, for example, various types of lighting, computers, in-vehicle displays, outdoor displays, household equipment, commercial equipment, home appliances, traffic-related displays, and clock displays. Can be suitably used in various fields including a display device, a calendar display device, a luminescent screen, and an acoustic device.

DESCRIPTION OF SYMBOLS 1 Base material 2 Fine particle layer 3 Barrier layer 4 Electrode 5 Organic layer 6 Electrode 7 Sealing can 8 Flattening layer 9 Concavity and convexity layer 10 Glass substrate 11 Inorganic sealing layer 12 Adhesive layer 13 Base material (PET)
14 Barrier layer 15 Sealant 16 Filler with desiccant

Claims

A substrate for organic electroluminescence, comprising at least a barrier layer having a thickness unevenness of 10 nm to 1,000 nm and a fine particle layer containing fine particles.
2. The organic electroluminescent substrate according to claim 1, wherein the barrier layer has a multilayer structure in which an organic layer made of an organic material and an inorganic layer made of an inorganic material are alternately laminated.
The organic electroluminescent substrate according to claim 2, wherein the total number of laminated layers of the organic layer and the inorganic layer is 2 or more.
4. The organic electroluminescent element substrate according to claim 1, wherein the fine particles have an average particle size of 0.5 μm to 10 μm.
5. The organic electroluminescence substrate according to claim 1, wherein the volume filling rate of the fine particles in the fine particle layer is 30% to 80%.
6. The organic electroluminescence substrate according to claim 1, wherein the light emission surface of the fine particle layer is flat or has a flattening layer on the light emission surface of the fine particle layer.
The substrate for organic electroluminescence according to any one of claims 1 to 6, further comprising a substrate, wherein the material of the substrate is either polyethylene terephthalate or polyethylene naphthalate.
An organic electroluminescent device comprising the organic electroluminescent substrate according to any one of claims 1 to 7.
In the CIE color system, the chromaticity x is 0.01 to 0.05 and the chromaticity y is 0.01 to 0 from the target chromaticity in the state before providing the fine particle layer in the organic electroluminescence substrate. The organic electroluminescent device according to claim 8, wherein the organic electroluminescent device is set to be larger than 0.05.