JP5754912B2 - Light extraction sheet, organic electroluminescent device, and method for manufacturing the same - Google Patents

Description

  The present invention relates to a light extraction sheet, an organic electroluminescent device, and a method for manufacturing the organic electroluminescent device.

  The organic electroluminescent device is a self-luminous display device and is expected to be used for displays and illumination. 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, various studies have been attempted in order to improve the light extraction efficiency.
For example, Patent Document 1 discloses an organic electroluminescence element in which a diffusion layer in which at least two kinds of fine particles having an average particle diameter different by one digit or more are dispersed in a resin is provided adjacent to a transparent electrode on the light extraction surface side. Proposed.
However, in this proposal, if the diffusion layer is formed directly on the substrate, problems such as contamination (contamination) of the substrate occur, and a drying process is required, which affects the tact time difference from the organic electroluminescent layer lamination process. However, it is not preferable in the process.
Patent Document 2 proposes that a low refractive index layer is disposed on the substrate side to increase the light extraction efficiency. However, as in this proposal, if the refractive index difference is large, total reflection is still generated, and light extraction from the organic electroluminescent layer becomes inefficient.
In the said patent documents 1 and 2, since the barrier layer is not provided, there exists a subject that generation | occurrence | production of the gas from the fine particle layer etc. and a water | moisture content cannot be suppressed.
Further, Patent Document 3 proposes a particle-dispersed resin sheet containing a particulate light diffusing agent, the light diffusing agent is unevenly distributed on one surface side of the resin sheet, and a gas barrier layer is provided. It is described that it contains.
However, in this proposal, the refractive index of each layer of the resin sheet is not optimized, and a refractive index step between the respective layers is generated, so that the light extraction efficiency is not sufficiently improved. Originally, this proposal does not intend to arrange a resin sheet between the substrate and the transparent substrate in the organic electroluminescent device, that is, inside (inside) the substrate of the organic electroluminescent device.

  Accordingly, a light extraction sheet, an organic electroluminescence device, and an organic electric field that have an adhesive layer, a base material, a fine particle layer, and a barrier layer in this order, and can reduce the refractive index step between the respective layers to increase the light extraction efficiency. At present, it is desired to provide a method for manufacturing an organic electroluminescent device that can efficiently manufacture the light emitting device with a simple process.

JP 2005-190931 A Japanese Patent No. 4186688 JP 2004-109497 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention includes a light extraction sheet that has at least an adhesive layer, a base material, a fine particle layer, and a barrier layer in this order, and that can reduce the refractive index step between the layers and increase the light extraction efficiency, and the light. It is an object of the present invention to provide an organic electroluminescent device using a take-out sheet and an organic electroluminescent device manufacturing method capable of efficiently manufacturing the organic electroluminescent device by a simple process.

Means for solving the problems are as follows. That is,
<1> It has at least an adhesive layer, a substrate, a fine particle layer, and a barrier layer in this order,
The light extraction sheet, wherein the refractive index of each layer is equal to or increases from the adhesive layer toward the barrier layer, and the maximum refractive index difference between adjacent layers is 0.2 or less.
<2> Light is applied to the surface of the substrate on the organic electroluminescent layer side in the organic electroluminescent device including the substrate, an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on the substrate. It is a light extraction sheet | seat as described in said <1> arrange | positioned so that the contact bonding layer of an extraction sheet | seat may contact | connect.
<3> The light extraction sheet according to any one of <1> to <2>, 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 laminated.
<4> The light extraction sheet according to any one of <1> to <3>, wherein the barrier layer has a refractive index of 1.7 or more.
<5> The light extraction sheet according to any one of <1> to <4>, wherein the surface of the fine particle layer on the barrier layer side is flat or has a flattening layer between the fine particle layer and the barrier layer. .
<6> The light extraction sheet according to <5>, wherein the planarization layer contains fine particles having an average particle diameter of 100 nm or less and a refractive index of 1.8 or more.
<7> An adhesive layer, a base material, a fine particle layer, a planarization layer, and a barrier layer are provided in this order, and the refractive index of each layer is equal to or increases from the adhesive layer toward the barrier layer. The light extraction sheet according to any one of <5> to <6>, wherein the maximum refractive index difference is 0.2 or less.
<8> The material according to any one of <1> to <7>, wherein the base material is any one of a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyethersulfone (PES) film. It is a light extraction sheet.
<9> An organic electroluminescent device comprising a substrate, an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on the substrate,
At least one of the anode and the cathode is a transparent electrode,
An organic electroluminescence device comprising the light extraction sheet according to any one of <1> to <8> between the substrate and the transparent electrode.
<10> A substrate, an adhesive layer, a base material, a fine particle layer, a barrier layer, and an organic electroluminescent layer are provided in this order, and the refractive index of each layer is equal to or increased from the substrate toward the organic electroluminescent layer, and The organic electroluminescence device according to <9>, wherein the maximum refractive index difference between adjacent layers is 0.2 or less.
<11> A method for producing an organic electroluminescent device comprising an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on a substrate,
A method for producing an organic electroluminescent device, wherein the adhesive layer of the light extraction sheet according to any one of <1> to <8> is attached to a surface of the substrate on the organic electroluminescent layer side.

  According to the present invention, the conventional problems can be solved, and at least the adhesive layer, the base material, the fine particle layer, and the barrier layer are provided in this order, and the refractive index step between the respective layers is reduced to increase the light extraction efficiency. It is possible to provide a light extraction sheet that can be manufactured, an organic electroluminescence device using the light extraction sheet, and an organic electroluminescence device manufacturing method that can efficiently manufacture the organic electroluminescence device by a simple process.

FIG. 1 is a schematic view showing an example of the light extraction sheet of the present invention. FIG. 2 is a diagram illustrating the fine particle layer, the planarization layer, and the barrier layer in the light extraction sheet. FIG. 3 is another diagram illustrating the fine particle layer, the planarization layer, and the barrier layer in the light extraction sheet. FIG. 4 is still another view showing the fine particle layer, the planarization layer, and the barrier layer in the light extraction sheet. FIG. 5 is a schematic view showing an example of the organic electroluminescent device of the present invention. FIG. 6 is a schematic diagram illustrating an example of a comparative organic electroluminescent device. FIG. 7 is a diagram illustrating a method for measuring the water vapor transmission rate of the light extraction sheet. FIG. 8 is a diagram showing the state of the light emitting surface on the first day in the left diagram in the evaluation of durability, and the state of the light emitting surface after seven days in the right diagram.

(Light extraction sheet)
The light extraction sheet of the present invention has at least an adhesive layer, a substrate, a fine particle layer, and a barrier layer in this order, and further has other layers as necessary.
As will be described later, the light extraction sheet preferably has a flat surface on the barrier layer side of the fine particle layer or a flattened layer between the fine particle layer and the barrier layer.

  The light extraction sheet is preferably disposed inside an organic electroluminescent device, and includes a substrate, an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on the substrate. More preferably, the organic electroluminescent device is disposed such that the adhesive layer of the light extraction sheet is in contact with the surface of the substrate on the organic electroluminescent layer side.

In the present invention, the light extraction sheet has an adhesive layer, a base material, a fine particle layer, and a barrier layer in this order, and preferably has a planarization layer between the fine particle layer and the barrier layer. It is preferable that the refractive indexes of the respective layers increase or decrease toward the barrier layer, and the maximum refractive index difference between adjacent layers is 0.2 or less and preferably 0.18 or less.
When the maximum refractive index difference exceeds 0.2, Fresnel reflection between layers becomes strong, and light extraction efficiency may decrease.
Here, the refractive indexes of the adhesive layer, the substrate, the fine particle layer, and the barrier layer can be measured by, for example, an ellipsometer.

<Barrier layer>
The light extraction sheet according to the present invention has a barrier layer for the purpose of preventing permeation of oxygen and moisture from the outside and the inside of the barrier layer of the light extraction sheet and the fine particle layer between the substrates. .
There is no restriction | limiting in particular as said barrier layer, What is necessary is just to select suitably according to the objective, The organic layer consisting of an organic material alone, or the inorganic layer consisting of an inorganic material may be single, but the organic layer consisting of an organic material And a multilayer structure in which an inorganic layer made of an inorganic material is laminated.
Examples of the inorganic materials, for example _{SiNx, SiON, SiO 2, Al} 2 O 3, etc. TiO ₂ and the like.
Examples of the organic material include a silicone polymer, an epoxy polymer, an acrylic polymer, and a urethane polymer.

There is no restriction | limiting in particular as a formation method of the said barrier layer, According to material, it can select suitably, For example, the apply | coating method, CVD method, a vacuum evaporation method, a sputtering method etc. are mentioned.
The refractive index of the barrier layer (average refractive index in the case of a multilayer structure) is preferably 1.7 or more, and more preferably 1.8 to 2.2. When the refractive index of the barrier layer is less than 1.7, the total reflection of light from the organic electroluminescent layer increases at the interface between the transparent electrode and the barrier layer, and the light extraction efficiency may decrease.
The refractive index of the barrier layer is preferably equal to or higher than the refractive index of the fine particle layer (or the planarizing layer), and preferably equal to or lower than the refractive index of the organic electroluminescent layer.
Here, the relationship between the refractive index of the barrier layer and the adjacent transparent electrode is not observed because the transparent electrode is very thin (below the wavelength of light, exuding effect), Presumed not to contribute. In addition, the refractive index of the transparent electrode is high, and it is necessary to increase the refractive index of the binder to about “2.1”. However, since it is not realistic to increase the refractive index by a simple method, it is excluded (ignored). doing.
Therefore, the refractive index of the barrier layer is more preferably as high as that of the transparent electrode.
As for the optical properties of the barrier layer, the light transmittance is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
The average thickness of the barrier layer (in the case of a multilayer structure, the total average thickness) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 μm to 10 μm, preferably 0.1 μm -5 μm is more preferable, and 0.2 μm to 3 μm is still more preferable. When the thickness of the barrier layer is less than 0.1 μm, the sealing function for preventing the permeation of oxygen and moisture in the atmosphere may be insufficient. When the thickness exceeds 10 μm, the light transmittance decreases and the transparent layer becomes transparent. When the inorganic material is used as a single layer, there is a possibility that the barrier properties such as cracking due to stress difference and peeling from the adjacent layer may be impaired.

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

<< 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, crosslinked 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. 58-2.1 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 a precision spectrometer (GMR-1DA, Shimadzu Corporation). ) And can be measured by the Shribsky method.

The average particle diameter 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%, and more preferably 40% to 70%. If the volume filling factor is less than 30%, the probability that 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 particles is measured with a particle specific gravity measuring device (MARK3, manufactured by Union Engineering Co., Ltd.), and the weight of 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 off, 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, and more preferably 2.4 to 3.0. The average particle size of the primary particles is preferably 0.5 nm to 100 nm, more preferably 1 nm to 80 nm, and particularly 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.
The particle diameter of the high refractive index fine particles is represented by an average primary particle diameter according to a 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 oxides such as Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, and Y, complex oxides, and sulfides. The particle | grains which have 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 and indium oxide, it is preferable to contain an 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 is more preferable, 0.3% to 5% by mass is particularly preferable, and 0.5% to 3% by mass is most preferable.
The contained elements Co, Al and Zr are present inside or on the surface of the high refractive index fine particles mainly composed of 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 whose refractive index of the oxide is 1.95 or more include Ta, Zr, In, Nd, Sb, Sn, Bi, and the like. 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. To 0.05 mass% to 10 mass%, more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.3 mass% to 3 mass%.

  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 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.

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

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 an affinity for 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 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 phosphate triacrylate, etc.}, alkanolamines {ethylenediamine EO adduct (5 mol), etc.}

  As said coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent etc. are contained. 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. 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.

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 can be appropriately selected according to the purpose, but is preferably in a range in which 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 (such as 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, a crosslinking reaction or a polymerization reaction of a curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer) is performed by at least one of heating and light irradiation. The method to make it occur 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 fine particle layer composition is applied.

  The binder in the cured film produced in this way is, for example, a curable polyfunctional monomer or polyfunctional oligomer, which is a precursor of the dispersant, and the 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 a vinyl chloride-vinyl copolymer resin, a polyacrylic resin, a polymethacrylic resin, a polyolefin resin, a urethane resin, a silicone resin, and an 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 Resins, amino alkyd resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins and the like can be mentioned.
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 cationic 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 necessary for these reactive curable resins, a crosslinking agent (epoxy compound, polyisocyanate compound, polyol compound, polyamine compound, melamine compound, etc.), polymerization initiator (azobis compound, organic peroxide compound, organic halogen compound, Conventionally known compounds such as curing agents such as 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” (Taiseisha, published in 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 which 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 ethylenically unsaturated groups 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. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. 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 a nucleophilic substituent such as hydroxyl group, amino group and mercapto group 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. Examples of polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include those described in paragraph numbers [0026] to [0027] of JP-A No. 2001-139663. Compounds.

  Examples of 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 ester group, 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 No. 54-21726.

  Furthermore, vinylurethane 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 A urethane compound having a diol (Japanese Examined Patent Publication No. Sho 62-39418), polyester acrylates (Japanese Examined Patent Publication No. Sho 52-30490, etc.), and further described in Journal of Japan Adhesion Association Vol. 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 cation polymerizable group-containing compound (hereinafter also referred to as “cation polymerizable compound” or “cation 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, and more preferably 2 to 5. The weight 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 weight average molecular weight is equal to or higher than the lower limit, there is no inconvenience such as a problem of volatilization during the film formation process. If the weight average molecular weight is equal to or lower than the upper limit, the compatibility with the composition for the fine particle layer is not caused. 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, homopolymers and copolymers of glycidyl acrylate and 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-11-242101, and paragraphs [0044] to [0046] of JP-A-10-158385. And the compounds described.

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

  Examples of the cyclic thioether compound include compounds having a thioepoxy ring instead of the epoxy ring of the epoxy compound.

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

  Examples of the spiro orthoester 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.}, isopropenyl compound {"J. Polymer Science: Part A: Polymer Chemistry ", Vol. 34, page 2051 (1996), etc.}. You may use these in combination of 2 or more types as appropriate.

  The polyfunctional compound is preferably a compound containing at least one of each selected from the radical polymerizable group and the cationic polymerizable group in the molecule. 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 cationic 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 It is more preferable to contain in the 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 is preferably a compound that generates radicals or acids upon irradiation with light and / or heat. The photopolymerization initiator preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. 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 or a compound having a bond with a small bond dissociation energy 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 (JP-A 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 a radical photopolymerization initiator such as an organic halogenated compound, a carbonyl compound, and an organic boric acid compound, etc., and disulfone compounds (JP-A-5-239015, JP-A-61-166544, etc.).

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull. Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, 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 preferable examples include 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], paragraphs [0015] to [0016] of JP-A-8-134404, Examples include the 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, the compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539 can be mentioned. 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. As addition amount, it is preferable that it is 0.1 mass%-30 mass% with respect to radical polymerization monomer whole quantity, It is more preferable that it is 0.5 mass%-25 mass%, 1 mass%-20 mass% % Is more preferable. 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] to JP-A-2002-29162. And the compounds described in [0059].

  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 [0035] of JP-A-9-268205, and paragraphs [0010] to [0011] of JP-A-2000-71366. A diaryl iodonium salt or a triarylsulfonium salt described in JP-A-2001-288205, a sulfonium salt of thiobenzoic acid S-phenyl ester described in JP-A-2001-288205, a paragraph number in JP-A-2001-133696 Examples include the onium salts described in [0030] to [0033].

  Other examples of the photoacid generator include organic metal / 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 cationic 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.

  When the polymerization reaction is carried out by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination with the fine particle layer composition. Examples of these sensitizers include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

  Moreover, when performing a polymerization reaction 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. Furthermore, a value having absorption in the region of 750 nm to 1,400 nm and a molecular extinction coefficient of 20,000 or more is preferable. Moreover, it is more preferable that there is a trough of absorption 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. Commercially available dyes and literature {for example, “Chemical Industry”, May 1986, pages 45-51, “Near-Infrared Absorbing Dye”, “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 Co., Ltd.], 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 and 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, alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are particularly preferable. A preferred organometallic compound is an organosilicon compound represented by the following general formula (2) and 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.

Formula (2): (R ²¹ ) _β- Si (Y ²¹ ) _4-β
However, In the general formula ^{(2), R 21} represents a substituted or unsubstituted C 1-30 aliphatic group or an aryl group having 6 to 14 carbon atoms. Y ²¹ represents a halogen atom (a chlorine atom, a bromine atom, etc.), an OH group, an OR ²² group, or an 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 preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms. Examples of the aryl group for R ²¹ include phenyl, naphthyl, anthranyl and the like, and a phenyl group is preferable.

  The substituent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, halogen (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, Ethyl, i-propyl, propyl, t-butyl, etc.), aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy) Etc.), aryloxy (phenoxy etc.), alkylthio group (methylthio, ethylthio etc.), arylthio group (phenylthio etc.), alkenyl group (vinyl, 1-propenyl etc.), alkoxysilyl group (trimethoxysilyl, triethoxysilyl etc.) , Acyloxy groups {acetoxy, (meth) acryloyl etc.}, alcohol Sicarbonyl group (methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), Acylamino groups (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 (acrylamino, methacrylamino). 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, based on the total solid content of the composition for fine particle layer. It is still more preferable that it is% -50 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. It is preferable that the binder has a silanol group because the physical strength, chemical resistance, and weather resistance of the fine particle layer are further improved. 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, or 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 of β-diketones and β-ketoesters. Specific examples include compounds described in paragraph numbers [0071] to [0083] in JP-A No. 2000-275403.

  The proportion 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 0.5% by mass to the organometallic compound. 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. Examples thereof include alcohols, ketones, esters, amides, ethers, ether esters, aliphatic hydrocarbons, halogenated carbons. Hydrogen etc. are mentioned. 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.), ester ( For example, 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), aromatic Group hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg, dioxane) Emissions, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (such as 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 (a curable polyfunctional monomer or polyfunctional oligomer having a specific polar group) as a cured film forming component in the fine particle layer composition. 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. Or a polyfunctional oligomer and / or an organosilicon compound represented by the general formula (2) is obtained by crosslinking or polymerization reaction.

  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, a polyfunctional monomer or a polyfunctional oligomer and a crosslinking reaction or a polymerization reaction to form a binder to maintain good and uniform dispersibility of the fine particles in the fine particle layer, thereby improving the physical strength and 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, and an extrusion coating method. It can be produced by applying a known thin film forming method such as, 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 a wavelength of 350 nm to 420 nm may be irradiated as a multi-beam. 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 from 0.1mW / cm ² ~100mW / cm 2 or so, an amount of light irradiation on the coating film ^{surface, 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.) to determine the average thickness of the fine particle layer.

The refractive index of the fine particle layer is preferably 1.7 to 2.2.
The refractive index of the fine particle layer is preferably equal to or higher than the refractive index of the adjacent substrate, and is preferably equal to or lower than the refractive index of the barrier layer (or planarization layer).

  It is preferable that the light emitting surface of the fine particle layer is flat or has a flattening layer on the light emitting surface of the fine particle 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. Furthermore, there is an advantage that a reduction in barrier performance of the barrier layer can be suppressed by planarization. When a barrier layer is laminated on a non-planar surface, gaps or pinholes due to steps are formed in the barrier layer, and the barrier performance may be significantly reduced.

  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. .

-Flattening layer-
The planarizing layer preferably has a composition that does not include the scattering fine particles in the fine particle layer, or the same composition as the organic layer of the barrier layer, and is similar to the fine particle layer or the organic layer of the barrier layer. Can be formed.
There is no restriction | limiting in particular in the thickness of the said planarization layer, Although it can select suitably according to the objective, It is preferable that they are 2 micrometers-50 micrometers. When the thickness of the flattening layer is less than 2 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.
The refractive index of the planarizing layer is preferably 1.7 to 2.2.
The planarization layer preferably has a refractive index equal to or higher than that of the fine particle layer, and preferably equal to or lower than that of the barrier layer.

-Base material-
The shape, structure, size, material and the like of the substrate are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a flat plate shape and the structure. As for, a single layer structure may be sufficient and a laminated structure may be sufficient, and the said magnitude | size can be suitably selected according to the magnitude | size etc. of the said light extraction sheet | seat.

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 refractive index of the substrate is preferably 1.5 to 1.7.
The refractive index of the substrate is preferably equal to or higher than the refractive index of the adhesive layer, and preferably equal to or lower than the refractive index of the fine particle layer.

-Adhesive layer-
Examples of the material for the adhesive layer include polymethyl methacrylate (PMMA), polyethylene, polyisobutene, polybutadiene, polyisoprene, polyacrolein, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, UV curable epoxy resin, thermosetting epoxy resin, and UV curable acrylic. Examples thereof include resins, polycarbonate resins, polyester resins, polystyrene resins, polyimide resins, ethylhexyl acrylate, butyl acrylate, and styrene.
The method for forming the adhesive layer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include knife coating, roll coating, curtain coating, spin coating, bar coating, dip coating, and spray coating. The method of apply | coating by either application | coating method is mentioned. A thermosetting or thermoplastic adhesive sheet can also be used.
There is no restriction | limiting in particular as average thickness of the said contact bonding layer, According to the objective, it can select suitably, 10 micrometers-200 micrometers are preferable.
The refractive index of the adhesive layer is preferably 1.4 to 1.7.
The refractive index of the adhesive layer is preferably equal to or higher than the refractive index of the substrate, and preferably equal to or lower than the refractive index of the base material.

The barrier layer in the light extraction sheet of the present invention is intended to shield the residual components of water vapor and gas generated from the fine particle layer and the flattening layer, thus covering moisture and gas intrusion from the outside of the organic electroluminescent device. The barrier performance is not necessary.
The water vapor transmission rate of the light extraction sheet 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 using 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 the light extraction sheet is preferably 10 cc / m ² / day or less, and more preferably 1 cc / m ² / day or less.
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).

FIG. 1 is a schematic view showing an example of the light extraction sheet of the present invention. The light extraction sheet 20 in FIG. 1 has an adhesive layer 2, a base material 3, a fine particle layer 4, a planarization layer 5, and a barrier layer 6 in this order.
As shown in FIG. 2, the fine particle layer 4, the planarization layer 5, and the barrier layer 6 are formed by forming an inorganic barrier layer 21 on the fine particle layer 4 and the flattening layer 5, as shown in FIG. A mode in which the inorganic barrier layer 21, the organic barrier layer 22, and the inorganic barrier layer 21 are formed on the layer 4 and the planarizing layer 5, as shown in FIG. And an embodiment in which the inorganic barrier layer 21, the organic barrier layer 22, and the inorganic barrier layer 21 are formed.

  The light extraction sheet of the present invention has at least an adhesive layer, a base material, a fine particle layer, and a barrier layer in this order, and can reduce the refractive index step between each layer and increase the light extraction efficiency. Although it can be used for a light emitting device or the like, it is particularly preferably used for the following organic electroluminescent device of the present invention.

(Organic electroluminescent device)
The organic electroluminescent device of the present invention comprises a substrate, an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on the substrate,
At least one of the anode and the cathode is a transparent electrode,
The light extraction sheet according to the present invention is provided between the substrate and the transparent electrode. It is preferable that the surface on the organic electroluminescent layer side of the substrate is in contact with the adhesive layer in the light extraction sheet.
In the present invention, a substrate, an adhesive layer, a base material, a fine particle layer, a barrier layer, and an organic electroluminescent layer are provided in this order, and the refractive index of each layer increases or decreases from the substrate toward the organic electroluminescent layer. And the maximum refractive index difference between adjacent layers is 0.2 or less. Thereby, the refractive index level difference between the respective layers can be reduced and the light extraction efficiency can be increased.

-Board-
There is no restriction | limiting in particular about the material of the said board | substrate, a structure, a structure, a magnitude | size, According to the use of a light emitting element, the objective, etc., it can select suitably. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members. The substrate may be transparent or opaque, and if transparent, it may be colorless and transparent or colored and transparent.

  There is no restriction | limiting in particular as a material of the said board | substrate, According to the objective, it can select suitably, For example, inorganic materials, such as a yttria stabilized zirconia (YSZ) and glass (an alkali free glass, soda-lime glass, etc.); Polyethylene Examples thereof include polyesters such as terephthalate, polybutylene phthalate, and polyethylene naphthalate; organic materials such as polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin, and poly (chlorotrifluoroethylene).

  The refractive index of the substrate varies depending on the material used and cannot be defined unconditionally. For example, in the case of glass, it is preferably 1.5 to 1.6.

-Organic electroluminescent layer-
The organic electroluminescent layer has at least a light emitting layer. Examples of the functional layer other than the light emitting layer 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 dry film forming methods such as vapor deposition and sputtering, wet coating methods, transfer methods, printing methods, and ink jet methods.

--- 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 purpose, but is preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm from the viewpoint of external quantum efficiency, More preferably, the thickness is 5 nm to 100 nm. Moreover, the said light emitting layer may be 1 layer, or may be two or more layers, and each layer may light-emit with a different luminescent color.

--- Luminescent material ---
As the light emitting material, any of a phosphorescent light emitting material, a fluorescent light emitting material and the like can be suitably used.
The light emitting material 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>ΔEa> with the host compound. A dopant satisfying the relationship of 0.2 eV is preferable from the viewpoint of driving durability.
The light emitting material in the light emitting layer is contained 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 in the light emitting layer. From the viewpoint, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 50% by mass.

<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. Rhenium, iridium, and platinum are more preferable, and iridium and platinum are more preferable.

  Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H.C. Examples include ligands described in Yersin's "Photochemistry and Photophysics of Coordination Compounds" published by Springer-Verlag 1987, Akio Yamamoto "Organic Metal Chemistry-Fundamentals and Applications-" .

  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, JP2002-2002 34894, 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 thereof 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 , A Pt complex, or a Re complex is more preferable, and an Ir complex, a Pt complex, or a Re complex including at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a 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 light emitting material is not particularly limited and may be appropriately selected depending on the purpose. For example, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin , Pyran, perinone, oxadiazole, aldazine, pyridine, 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, various metal complexes represented by pyromethene complexes and rare earth complexes, polythiophene Polyphenylene polymer 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, oxadiazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluoreni Heterocyclic tetracarboxylic anhydrides such as redenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, naphthaleneperylene, phthalocyanines, or derivatives thereof (may form condensed rings with other rings), 8-quinolinol derivatives And various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazole as a ligand. 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 No. 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, And the like.

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. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. It is further more preferable and it is especially preferable that it is 0.1 mass%-10 mass%.

  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. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high 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, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles 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, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 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. The hole blocking layer and the electron blocking layer may have a single-layer structure made of one or more of the materials described above, or a multilayer structure made up of a plurality of layers having the same composition or different compositions. Also good.

--- 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.

  There is no restriction | limiting in particular as said electrode, Although it can select suitably according to the objective, It is preferable to comprise the said reflecting metal and the translucent metal as said translucent member in the anode and cathode.

  Specific examples of the material constituting the anode include, for example, tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (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. Examples include alloys, lithium-aluminum alloys, magnesium-silver alloys, 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, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injection properties, and materials mainly composed of aluminum are 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.).

  There is no restriction | limiting in particular about the formation method of the said electrode, According to a well-known method, it can carry out. 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 using a laser or the like. It may be performed by sputtering or the like, or may be performed by a lift-off method or a printing method.

Here, FIG. 5 is a schematic view showing an example of the organic electroluminescent device of the present invention. The organic electroluminescent device of FIG. 5 includes a light extraction sheet 20 composed of an adhesive layer 2, a base material 3, a fine particle layer 4, a planarizing layer 5, and a barrier layer 6, a substrate 1, a transparent electrode ( ITO) 7.
Therefore, the light extraction sheet 20, the transparent electrode 7, the organic electroluminescent layer 8, and the reflective electrode 9 are provided on the substrate 1, and these are sealed with the sealing can 10.

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 a full color type, for example, as described in “Monthly Display”, September 2000, pages 33 to 37, the three primary colors (blue (B), A three-color light emission method in which a layer structure that emits light corresponding to green (G) and red (R) is arranged on a substrate, a white light that divides white light emission by a layer structure for white light emission into three primary colors through a color filter layer And a color conversion method in which blue light emission by a layer structure for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer 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.

(Production Example 1)
-Production of planarization layer material 1-
Titanium oxide dispersed in toluene (average particle size 15 nm, material name: titanium oxide-dispersed toluene, product name: highly transparent titanium oxide slurry 760T, manufactured by Teica) 44 parts by mass, and resin material (material name) using toluene as a solvent : Fluorene derivative, trade name: Ogsol EA-0200, Osaka Gas Chemical Co., Ltd.) 55 parts by mass, polymerization initiator (material name: azo-based thermal polymerization initiator, trade name: V-65, Wako Pure Chemical Industries, Ltd.) The flattened layer material 1 was prepared by stirring and thoroughly mixing with 1 part by mass of a solution (made by company).

(Production Example 2)
-Production of fine particle layer material 1-
60% by mass of polystyrene-based fine particles (material name: melamine resin particles, trade name: Optobead 2000M, manufactured by Nissan Chemical Industries, Ltd.) is added to the planarization layer material 1 of Production Example 1, and stirring is continued. The fine particle layer material 1 was prepared by dispersing in the above.

(Production Example 3)
-Production of planarization layer material 2-
A planarization layer material 2 was produced in the same manner as in Production Example 1 except that the “highly transparent titanium oxide slurry 760T” was not used in the planarization layer material 1 of Production Example 1.

(Production Example 4)
-Production of fine particle layer material 2-
60% by mass of polystyrene fine particles (material name: melamine resin particles, trade name: Optobead 2000M, manufactured by Nissan Chemical Industries, Ltd.) is added to the planarizing layer material 2 of Production Example 3, and the stirring is continued. To prepare a fine particle layer material 2.

(Comparative Example 1)
-Production of light extraction sheet 1-
On a sufficiently washed polyethylene naphthalate (PEN) film (thickness: 100 μm, refractive index = 1.67), the fine particle layer material 1 of Production Example 2 was applied, heated and sufficiently cured, and an average thickness of 25 μm. A fine particle layer was formed. On this fine particle layer, the planarizing layer material 1 of Production Example 1 was applied and cured to form a planarizing layer having an average thickness of 10 μm.
Next, a double-sided optical tape (thickness 25 μm, material name: transparent adhesive sheet, product name: LUCIACS CS9621T, manufactured by Nitto Denko Corporation) is attached to the surface opposite to the surface of the PEN film on which the fine particle layer and the flattening layer are formed. I attached. The optical double-sided tape has an acrylic adhesive layer (refractive index = 1.51).
The light extraction sheet 1 of Comparative Example 1 was produced as described above.

(Comparative Example 2)
-Production of light extraction sheet 2-
In Comparative Example 1, a light extraction sheet 2 of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that the planarizing layer was not formed on the fine particle layer.

( Reference Example 1)
-Production of light extraction sheet 3-
Comparative Example 1 is the same as Comparative Example 1 except that an inorganic barrier layer (SiN, refractive index 1.80) having an average thickness of 300 nm is formed on the surface of the planarization layer by a CVD apparatus (manufactured by samco, CCP-CVD). Similarly, a light extraction sheet 3 having the barrier layer (1) of Reference Example 1 was produced.

(Example 2)
-Production of light extraction sheet 4-
In Comparative Example 1, an inorganic barrier layer (SiN, refractive index 1.80) having an average thickness of 100 nm was formed on the planarizing layer surface by a CVD apparatus (manufactured by samco, CCP-CVD), and then the inorganic barrier layer On top of this, an organic barrier layer having an average thickness of 1,000 nm was formed as follows, and then an inorganic barrier layer (SiN, refractive index 1.80) having an average thickness of 100 nm was formed by the CVD apparatus. Except for this, a light extraction sheet 4 having the barrier layer (2) of Example 2 was produced in the same manner as in Comparative Example 1.

-Formation of organic barrier layer composition and organic barrier layer-
A composition comprising a polymerizable compound (total 20 parts by mass) shown in Table 1 below, a polymerization initiator (Lamberti, Ezacure KTO46), and titanium oxide fine particles (Taika, MT-100HD), A film was prepared with methyl ethyl ketone so as to have an average thickness of 1,000 nm, and cured by irradiation with an ultraviolet ray irradiation amount of 1.2 J / cm ² in an atmosphere of oxygen of 100 ppm to produce an organic barrier layer containing fine particles.

<Polymerizable compound F-1>
<Polymerizable compound F-2>
<Polymerizable compound F-3>
<Polymerizable compound F-4>

(Example 3)
-Production of light extraction sheet 5-
In Comparative Example 2, an organic barrier layer having an average thickness of 1,000 nm (also serving as a planarizing layer) was formed on the fine particle layer in the same manner as in Example 2. Next, in the same manner as in Example 2. The barrier of Example 3 was the same as Comparative Example 2 except that an inorganic barrier layer having an average thickness of 100 nm, an organic barrier layer having an average thickness of 1,000 nm, and an inorganic barrier layer having an average thickness of 100 nm were sequentially formed. A light extraction sheet 5 having a layer (3) was produced.

(Comparative Example 3)
-Production of light extraction sheet 6-
In Example 3, a polyethylene naphthalate (PEN) film (thickness 100 μm, refractive index = 1.67) was replaced with an acrylic film (thickness 100 μm, refractive index = 1.49) in the same manner as in Example 3. Thus, a light extraction sheet 6 having the barrier layer (3) of Comparative Example 3 was produced.

(Comparative Example 4)
-Production of light extraction sheet 7-
In Comparative Example 1, the fine particle layer material 1 is changed to the fine particle layer material 2 of Production Example 4, and the flattening layer material 1 is changed to the flattening layer material 2 of Production Example 3, and an ion plating apparatus is used on the flattening layer surface. A light extraction sheet 7 having the barrier layer (4) of Comparative Example 4 was prepared in the same manner as Comparative Example 1 except that an inorganic barrier layer (SiO ₂ , refractive index 1.45) having an average thickness of 300 nm was formed. did.

Table 2 summarizes the layer configuration of each of the light extraction sheets of Reference Example 1, Examples 2 to 3 and Comparative Examples 1 to 4 that were produced.
About each light extraction sheet | seat, the water-vapor-permeation rate was measured as follows. The results are shown in Table 2. Moreover, the refractive index of each layer which comprises each light extraction sheet | seat was measured as follows. The results are shown in Table 2 with ().

<Measurement of water vapor transmission rate>
The water vapor transmission rate of each light extraction sheet is shown in FIG. 7 using 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). Thus, the light extraction sheet 20 was set, and the temperature was measured at 60 ° C. and the relative humidity was 90%. The results are shown in Table 2.

<Measurement of refractive index of each layer>
The refractive index of each layer constituting the light extraction sheet was measured using an ellipsometer (manufactured by JA Woollam Japan).

* The value in () in Table 2-1 indicates the refractive index.
* In Example 3, the organic barrier layer also functions as a planarization layer.
* The value in () in Table 2-2 indicates the refractive index.

From the results in Table 2, it was found that the light extraction sheets of Reference Example 1, Examples 2 to 3 and Comparative Example 3 can obtain sufficient barrier performance.
On the other hand, in Comparative Examples 1 and 2, it was found that the water vapor transmission rate was not in a preferable range and the barrier performance was inferior.

( Reference Example 4)
-Fabrication of organic electroluminescence device-
Using the light extraction sheet 3 [adhesive layer / PEN film / fine particle layer / flattening layer / barrier layer (1)] prepared in Reference Example 1, an organic electroluminescence device of Reference Example 4 was prepared as follows. .

First, a glass substrate (manufactured by Corning, Eagle XG, refractive index 1.51) is placed in a washing container, ultrasonically washed in a neutral detergent, then ultrasonically washed in pure water, and heated at 120 ° C. for 120 minutes. Drying was performed.
Next, the light extraction sheet 3 was attached to one surface of the substrate from the adhesive layer side.
Next, an ITO (Indium Tin Oxide) film was formed to a thickness of 100 nm on the barrier layer of the light extraction sheet attached to the glass substrate 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 so as to have 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 a vacuum deposition method 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 as an electron transport layer on the white light-emitting 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 so as to have a thickness of 1 nm, and aluminum was deposited as an electrode layer on the buffer layer so as to have a thickness of 100 nm, thereby preparing a laminate.
The produced laminate was moved from 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, an organic electroluminescent device of Reference Example 4 was produced.

(Example 5)
-Fabrication of organic electroluminescence device-
Reference Example 4, the light extraction sheet 3, except that instead of the sheet 4 light extraction prepared in Example 2 [adhesive layer / PEN film / particle layer / planarizing layer / barrier layer (2)], Reference Example 4 In the same manner, an organic electroluminescent device of Example 5 was produced.

(Example 6)
-Fabrication of organic electroluminescence device-
Reference Example 4 except that the light extraction sheet 3 in Reference Example 4 was replaced with the light extraction sheet 5 [adhesive layer / PEN film / fine particle layer / flattening layer / barrier layer (3)] prepared in Example 3. In the same manner, an organic electroluminescent device of Example 6 was produced.

(Comparative Example 5)
-Fabrication of organic electroluminescence device-
In Reference Example 4, an organic electroluminescence device of Comparative Example 5 was produced in the same manner as Reference Example 4 except that the light extraction sheet 3 was not used.

(Comparative Example 6)
-Fabrication of organic electroluminescence device-
In Reference Example 4, the light extraction sheet 3 was not used, and the fine particle layer material 1 of Production Example 2 was applied onto the substrate, heated and sufficiently cured to form a fine particle layer having an average thickness of 25 μm. The organic electric field of Comparative Example 6 is the same as Reference Example 4 except that the flattening layer material 1 of Production Example 1 is applied on this fine particle layer and cured to form a flattening layer having an average thickness of 10 μm. A light emitting device was manufactured.

(Comparative Example 7)
-Fabrication of organic electroluminescence device-
In Reference Example 4, without using the light extraction sheet 3, the fine particle layer material 1 of Production Example 2 was applied on the substrate, heated and sufficiently cured to form a fine particle layer having an average thickness of 25 μm, and this On the fine particle layer, the flattening layer material 1 of Production Example 1 is applied and cured to form a flattening layer having an average thickness of 10 μm. Next, on this flattening layer, in the same manner as in Example 2. An inorganic barrier layer (SiN) having an average thickness of 100 nm is formed, an organic barrier layer having an average thickness of 1,000 nm is then formed on the inorganic barrier layer, and an inorganic barrier layer having an average thickness of 100 nm is then formed. An organic electroluminescent device of Comparative Example 7 was produced in the same manner as Reference Example 4 except that (SiN) was formed.

(Comparative Example 8)
-Fabrication of organic electroluminescence device-
Reference Example 4, except for changing the light extraction sheet 3 on the light extraction sheet 1 of Comparative Example 1, in the same manner as in Reference Example 4, to manufacture an organic electroluminescence device of Comparative Example 8.

(Comparative Example 9)
-Fabrication of organic electroluminescence device-
Reference Example 4, except for changing the light extraction sheet 3 on the light extraction sheet 2 of Comparative Example 2, in the same manner as in Reference Example 4, to manufacture an organic electroluminescence device of Comparative Example 9.

(Comparative Example 10)
-Fabrication of organic electroluminescence device-
Reference Example 4 except that the light extraction sheet 3 in Reference Example 4 was replaced with the light extraction sheet 6 [adhesive layer / acrylic film / fine particle layer / flattening layer / barrier layer (3)] prepared in Comparative Example 3. In the same manner, an organic electroluminescent device of Comparative Example 10 was produced.

(Comparative Example 11)
-Fabrication of organic electroluminescence device-
Reference Example 4, except that instead of the light extraction light extraction sheet 7 to produce a sheet 3 in Comparative Example 4 Adhesion layer / PEN film / particle layer / planarizing layer / barrier layer (4)] is a reference example 4 Similarly, an organic electroluminescent device of Comparative Example 11 was produced.

(Comparative Example 12)
-Fabrication of organic electroluminescence device-
In Reference Example 4, Comparative Example 12 was performed in the same manner as Reference Example 4 except that the light extraction sheet 3 was attached to the surface opposite to the organic electroluminescent layer side of the substrate of the organic electroluminescent device prepared in Comparative Example 5. An organic electroluminescent device was prepared (see FIG. 6).

Next, the light extraction efficiency and durability of each of the organic electroluminescent devices of Reference Example 4, Examples 5 to 6 and Comparative Examples 5 to 12 were measured as follows. The results are shown in Table 3.

<Measurement of luminance and calculation of light extraction efficiency>
The luminance was measured by applying a DC constant voltage to each organic electroluminescent device using a source measure unit 2400 type manufactured by Toyo Technica Corporation. The luminance was measured using a spectral luminance meter (SR-3 manufactured by Topcon Corporation) at a current value of 10 mA / cm ² .
The light extraction efficiency is defined by the following equation.
(Brightness of each reference example, example and comparative example / brightness of comparative example 5) × 100 = light extraction efficiency

<Durability evaluation method>
Immediately after the organic electroluminescent device was manufactured by the manufacturing method of the reference example, the example, and the comparative example, a certain amount of current was applied and turned on, and the surface state was observed (photographed with a digital camera). It was stored at a temperature of 60 ° C. for 7 days. After storage for 7 days, the organic electroluminescence device was turned on again by passing a certain amount of current, and the state of the surface was observed (photographed with a digital camera). The left side of FIG. 8 shows the light emitting surface on the first day, and the right side of FIG. 8 shows the light emitting surface after 7 days.
The image data taken by the digital camera was subjected to image analysis processing and the light emission area was measured.
The reason for performing the image analysis processing is that the light emitting surface is covered with a fine particle layer, so that the contours of the light emitting surface and the dark spot are difficult to see and difficult to measure.
The following formula is used as a method for calculating the dark spot area ratio including the shrink area: (1- (light emission area after 7 days / light emission area on the first day of photographing)) × 100 (%) = dark spot area ratio (%)
The smaller the value of the dark spot area, the smaller the damage to the organic electroluminescent element. As a reference, a dark spot area ratio of 2% or less was regarded as an acceptable line.

<Manufacturing efficiency of organic electroluminescent device>
The production efficiency of the organic electroluminescent device indicates whether the tact time is increased or decreased with respect to the following criteria when manufacturing the organic electroluminescent device from the substrate to the sealing in one line. Is. The tact time for manufacturing an organic electroluminescent device having no light extraction structure such as the light extraction sheet of Comparative Example 5 is used as a reference.
〔Evaluation criteria〕
○: When the tact time is equal to that of Comparative Example 5 ×: When the tact time is longer than that of Comparative Example 5
* The value in () in Table 3-1 indicates the refractive index.
* Values in () in Table 3-2 indicate refractive index.

* The value in () in Table 3-3 indicates the refractive index.
** In Comparative Example 12 in Table 3-3, the maximum refractive index difference is 0.16 in the notation order in the table, but the organic electroluminescent layer and the substrate are actually adjacent (via ITO). The configuration is the same as that of Comparative Example 5, and the maximum refractive index difference is 0.31.

  The light extraction sheet of the present invention and the organic electroluminescence device using the light extraction sheet are, for example, various types of lighting, a computer, an on-vehicle display, an outdoor display, a household device, a commercial device, a household appliance, and a traffic relationship. It can be suitably used in various fields including a display device, a clock display device, a calendar display device, a luminescent screen, and an acoustic device.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Adhesive layer 3 Base material 4 Fine particle layer 5 Flattening layer 6 Barrier layer 7 Transparent electrode 8 Organic electroluminescent layer 9 Reflective electrode 10 Sealing can 11 Sealing material 12 Ca
20 light extraction sheet 21 inorganic barrier layer 22 organic barrier layer

Claims (11)

It has at least an adhesive layer, a substrate, a fine particle layer, and a barrier layer in this order,
The barrier layer has a three-layer structure in which an inorganic layer made of an inorganic material, an organic layer made of an organic material, and an inorganic layer made of an inorganic material are laminated in this order, and the average thickness of the barrier layer is 0.1 μm. 10 μm, and the refractive index of the barrier layer is 1.7 or more,
A light extraction sheet, wherein the refractive index of each layer is equal to or increases from the adhesive layer toward the barrier layer, and the maximum refractive index difference between adjacent layers is 0.2 or less.   A light extraction sheet is provided on a surface of the substrate on the organic electroluminescent layer side in an organic electroluminescent device comprising an substrate, an anode, a cathode on the substrate, and an organic electroluminescent layer between the anode and the cathode. The light extraction sheet according to claim 1, wherein the light extraction sheet is disposed so that the adhesive layer is in contact therewith.   The light extraction sheet according to claim 1, wherein an average thickness of the barrier layer is 0.1 μm to 5 μm.   The light extraction sheet according to claim 1, wherein the barrier layer has a refractive index of 1.8 to 2.2.   The light extraction sheet according to any one of claims 1 to 4, wherein a surface of the fine particle layer on the barrier layer side is flat or has a flattening layer between the fine particle layer and the barrier layer.   The light extraction sheet according to claim 5, wherein the planarizing layer contains fine particles having an average particle diameter of 100 nm or less and a refractive index of 1.8 or more.   It has an adhesive layer, a substrate, a fine particle layer, a planarizing layer, and a barrier layer in this order, and the refractive index of each layer is equal to or increases from the adhesive layer toward the barrier layer, and the maximum refractive index between adjacent layers The light extraction sheet according to claim 5, wherein the difference is 0.2 or less.   The light extraction sheet according to any one of claims 1 to 7, wherein the substrate is any one of a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyethersulfone (PES) film. An organic electroluminescent device comprising a substrate, an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on the substrate,
At least one of the anode and the cathode is a transparent electrode,
An organic electroluminescent device comprising the light extraction sheet according to any one of claims 1 to 8 between the substrate and the transparent electrode.   A substrate, an adhesive layer, a base material, a fine particle layer, a barrier layer, and an organic electroluminescent layer are provided in this order, and the refractive index of each layer is equal to or increases from the substrate toward the organic electroluminescent layer, and adjacent layers The organic electroluminescent device according to claim 9, wherein the maximum refractive index difference is 0.2 or less. A method of manufacturing an organic electroluminescent device comprising an anode, a cathode, and an organic electroluminescent layer between the anode and the cathode on a substrate,
A method for producing an organic electroluminescent device, comprising: bonding an adhesive layer of the light extraction sheet according to claim 1 to a surface of the substrate on the organic electroluminescent layer side.