JP2009259802A - Light scattering layer transfer material, and organic el display device and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light scattering layer transfer material capable of efficiently forming a light scattering layer without giving damage to an organic EL display device, because it does not contain water and solvent, and to provide the organic EL display device using the same and having improved efficiency of light extraction and less brightness unevenness. <P>SOLUTION: The light scattering layer transfer material forms the light scattering layer on the negative electrode of the organic EL display device which has at least a luminescent layer between a positive electrode and the negative electrode. The transfer material has a temporary support, and at least the light scattering layer on the temporary support. The light scattering layer contains at least a translucent resin and light scattering particles, and the light scattering particles have an average particle size of 50-300 nm. In a preferred embodiment, a light-heat conversion layer exists between the temporary support and the luminescent layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  Since the present invention does not include water and a solvent, the light scattering layer transfer material capable of efficiently forming the light scattering layer without damaging the light emitting material of the organic electroluminescence display device (organic EL display device), The present invention also relates to an organic EL display device that is excellent in light extraction efficiency and has little luminance unevenness, and a method for manufacturing the organic EL display device.

  The organic EL display device is a self-luminous display device and is used for displays and illumination. This organic EL display device has an advantage of display performance that is higher in visibility than a conventional CRT or LCD and has no viewing angle dependency. There is also an advantage that the display can be reduced in weight and thickness. On the other hand, in addition to the advantages of lightening and thinning the organic EL lighting, there is a possibility of realizing lighting in a shape that could not be realized so far by using a flexible substrate.

  The organic EL display device has excellent characteristics as described above, but generally the refractive index of each layer constituting the display device including the light emitting layer is higher than that of air. For example, in an organic EL display device, the refractive index of an organic thin film layer such as a light emitting layer is 1.6 to 2.1. For this reason, the emitted light is likely to be totally reflected at the interface, the light extraction efficiency does not reach 20%, and most of the light is lost.

The light loss in the organic EL display device will be described with reference to FIG.
As shown in FIG. 1, the organic EL display basically has a back electrode 2, an organic layer 3 including two or three layers including a light emitting layer, a transparent electrode 4, and a transparent electrode on a TFT substrate 1. A structure in which the substrate 5 is laminated, and the holes injected from the back electrode 2 and the electrons injected from the transparent electrode 4 recombine in the organic layer 3 to emit light by exciting a fluorescent substance or the like. It is. Then, the light emitted from the organic layer 3 is reflected directly or by the back electrode 2 formed of aluminum or the like and is emitted from the transparent substrate 5.
However, as shown in FIG. 1, the light generated inside the display device is totally reflected depending on the angle of incidence on the adjacent layer interface having a different refractive index, and is guided out of the display device and taken out to the outside. Not possible (lights Lb and Lc in FIG. 1). The ratio of the guided light is determined by the relative refractive index with the adjacent layer, and is a general organic EL display device [air (n = 1.0) / transparent substrate (n = 1.5) / transparent electrode (n = 2.0) / organic layer (n = 1.7) / back electrode], the ratio of light that is not emitted to the atmosphere (air) but is guided inside the display device is 81%. That is, only about 19% of the total light emission amount can be effectively used.

For this reason, in order to improve the light extraction efficiency, (1) the light (Lb in FIG. 1) that is totally reflected at the air interface between the transparent substrate and the air and guided through the “organic layer + transparent electrode + transparent substrate” is extracted (2 1) A method for extracting light (Lc in FIG. 1) that is totally reflected at the interface between the transparent electrode and the transparent substrate and guided through the “organic layer and transparent electrode” is required. Among these, regarding (1), a method has been proposed in which irregularities are formed on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (see Patent Document 1).
Regarding (2), a method of processing the interface between the transparent electrode and the transparent substrate and the interface between the light emitting layer and the adjacent layer into a diffraction grating has been proposed (see Patent Document 2 and Patent Document 3).
Furthermore, a method has been proposed in which the interface between stacked organic layers is processed into irregularities to increase luminous efficiency (see Patent Document 4). Among them, in the method of forming a diffraction grating at the interface between the light emitting layer and the adjacent layer, the adjacent layer is made of a conductive medium, and the depth of the unevenness of the diffraction grating is about 40% with respect to the thickness of the light emitting layer, The guided light is extracted by making the pitch and depth of the irregularities have a specific relationship. Further, the method of forming irregularities at the interface between the organic layers is such that the layer adjacent to the irregularities is made of a conductive medium, the depth is about 20% with respect to the thickness of the light-emitting layer, and the angle of inclination of the interface is about 30 °. Is formed at the interface between the organic layers, and the bonding interface between the organic layers is increased to increase the luminous efficiency.
However, the above method is difficult to process and has problems such as easy breakdown due to energization, and further development of a useful light extraction method is desired for improving the efficiency of the organic EL display device. .

As one means for solving these problems, for example, means for improving the extraction efficiency by providing a light scattering layer on the surface of the organic EL surface light emitter has been proposed (see Patent Document 5 and Patent Document 6). . However, when light scattering occurs on the surface, there is a problem that light blur increases and resolution deteriorates.
On the other hand, a method has been proposed in which a light scattering layer is disposed immediately above the negative electrode to improve image extraction efficiency and reduce image blur (see Patent Document 7).
However, this proposed method uses a material having a refractive index of 1.5 to 1.6 as the base material of the light scattering layer, and the refraction for efficiently extracting the light guided through the organic layer and the transparent electrode. The rate was inappropriate.

  As a method for forming the light scattering layer as described above, a coating method is known. However, since the light emitting material of the organic EL display device is weak to water and a solvent, there is a restriction in terms of material, and the light scattering layer is formed. Efficient formation has the problem that it is difficult to put into practical use.

US Pat. No. 4,774,435 Japanese Patent Laid-Open No. 11-283951 JP 2002-31554 A JP 2002-31567 A JP 2003-109747 A JP 2003-173877 A JP 2006-107744 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, since the present invention does not include water and a solvent, the light scattering layer transfer material capable of efficiently forming the light scattering layer without damaging the light emitting material of the organic EL display device, and the light scattering layer An object of the present invention is to provide an organic EL display device that uses a transfer material and has excellent light extraction efficiency and little luminance unevenness, and a method for manufacturing the organic EL display device.

  As a result of intensive studies by the present inventors in order to solve the above problems, a temporary support and a light scattering layer transfer material having at least a light scattering layer and, if necessary, a photothermal conversion layer on the temporary support are used. As a result, a light-scattering layer that does not contain a solvent can be formed on the light-emitting layer of the organic EL display device, so that the light-emitting material is not damaged by the solvent and high luminance can be obtained. In addition, since the light scattering layer is not formed on the organic EL element but on the temporary support on which the light scattering layer is easily formed, unevenness due to uneven distribution of light scattering particles and unevenness due to variation in the thickness of the light scattering layer. It was found that is difficult to occur.

This invention is based on the said knowledge by this inventor, The means for solving the said subject are as follows. That is,
<1> A light scattering layer transfer material for forming a light scattering layer on the negative electrode in an organic EL display device having at least a light emitting layer between a positive electrode and a negative electrode,
A temporary support, and at least a light scattering layer on the temporary support;
The light scattering layer contains at least a translucent resin and light scattering particles;
The light scattering layer transfer material, wherein the light scattering particles have an average particle diameter of 50 nm to 300 nm.
<2> The light scattering layer transfer material according to <1>, wherein a light-heat conversion layer is provided between the temporary support and the light scattering layer.
<3> The light according to <2>, wherein the photothermal conversion layer contains at least one photothermal conversion material selected from molybdenum, chromium, gold, silver, copper, aluminum, and alloys thereof, and carbon black. It is a scattering layer transfer material.
<4> The light scattering layer transfer material according to any one of <1> to <3>, wherein the light scattering layer has a thickness of 0.5 μm to 5.0 μm.
<5> The light scattering layer transfer material according to any one of <1> to <4>, wherein a volume filling rate of light scattering particles in the light scattering layer is 10% or less.
<6> An organic EL display device having a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate,
An organic EL display device comprising a light scattering layer formed using the light scattering layer transfer material according to any one of <1> to <5> on the barrier layer.
<7> A method for producing an organic EL display device having a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate,
Manufacturing of an organic EL display device, wherein the light scattering layer transfer material according to any one of <1> to <5> is pasted by a laminator so that the light scattering layer side surface is in contact with the barrier layer Is the method.
<8> A method for producing an organic EL display device having a positive electrode, an organic EL layer including at least a light emitting layer, a negative electrode, and a barrier layer in this order on a glass substrate,
The light scattering layer transfer material according to any one of <2> to <5> is attached so that the surface on the light scattering layer side is in contact with the barrier layer, and light is irradiated from the temporary support side to the position of the light-to-heat conversion layer. A method of manufacturing an organic EL display device.

  According to the present invention, since the conventional problems can be solved and water and a solvent are not included, a light scattering layer transfer material capable of efficiently forming a light scattering layer without damaging the organic EL display device. In addition, it is possible to provide an organic EL display device that uses the light scattering layer transfer material and has excellent light extraction efficiency and little luminance unevenness, and a method for manufacturing the organic EL display device.

FIG. 1 is a diagram illustrating the cause of a decrease in light extraction efficiency in a self-luminous display device. FIG. 2 is a diagram showing an example of the configuration of the organic EL display device of the present invention. FIG. 3 is a view for explaining an example of transfer using the light scattering layer transfer material of the present invention. FIG. 4 is a diagram for explaining an example of laser transfer using the light scattering layer transfer material of the present invention.

Hereinafter, the light scattering layer transfer material of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Light scattering layer transfer material)
The light scattering layer transfer material of the present invention is a light scattering layer transfer material for forming a light scattering layer on the negative electrode in an organic EL device having at least a light emitting layer between a positive electrode and a negative electrode,
It has a temporary support, and at least a light scattering layer on the temporary support, and a light-to-heat conversion layer, a thermoplastic resin layer, a separation layer, a cover sheet, and other layers as necessary.

The light scattering layer transfer material includes, for example, a temporary support, and a thermoplastic resin layer, a separation layer, a light scattering layer, and a covering sheet in this order on the temporary support as a form of thermal transfer.
As a form of laser transfer, for example, a temporary support, and a photothermal conversion layer, a thermoplastic resin layer, a separation layer, a light scattering layer, and a covering sheet are provided in this order on the temporary support.

<Temporary support>
The temporary support may be chemically and thermally stable, may be made of a flexible material, and may have electrical conductivity for antistatic purposes.
As the temporary support, for example, a sheet of polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, triacetyl cellulose, or a laminate thereof is preferable.
The thickness of the temporary support is preferably 5 μm to 300 μm, and more preferably 20 μm to 150 μm.

Here, if the temporary support is peeled off after the light scattering layer of the light scattering layer transfer material is brought into close contact with the transfer target, the film and the human body may be charged and receive an unpleasant electric shock. Due to this charging, unexposed portions are generated in the subsequent exposure process by sucking dust from the surrounding area, which may cause pinholes. In the light scattering layer transfer material of the present invention, in order to prevent electrification, a conductive layer is provided on at least one surface of the temporary support so that the surface electric resistance is 10 ¹³ Ω or less, or the temporary support itself. It is preferable to use a material having conductivity imparted to a surface electrical resistance of 10 ¹³ Ω or less.

In order to impart conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of kneading metal oxide fine particles or an antistatic agent is suitable. Examples of the metal oxide include at least one crystalline metal oxide selected from zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide, and And / or fine particles of the composite oxide thereof.
Examples of the antistatic agent include alkyl phosphates (for example, electro stripper A manufactured by Kao Soap Co., Ltd., Elenon No. 19 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like as anionic surfactants. .
Examples of amphoteric surfactants include betaines (for example, Amogen K manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
Examples of nonionic surfactants include polyoxyethylene fatty acid ester-based (for example, Nissan Nonion L manufactured by NOF Corporation), polyoxyethylene alkyl ether-based (for example, Emulgen 106, 120, 147 manufactured by Kao Soap Co., Ltd.). , 420, 220, 905, 910, Nippon Oil & Fats Co., Ltd., Nipponsanonion E, etc.), polyoxyethylene alkylphenol ether type, polyhydric alcohol fatty acid ester type, polyoxyethylene sorbitan fatty acid ester type, polyoxyethylene alkylamine type Etc.

When a conductive layer containing a conductive substance is provided on the temporary support, the conductive substance is not particularly limited and can be appropriately selected from known ones. For example, ZnO , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO _3, at least one crystalline metal oxide and / or fine particles of its composite oxide, It is preferable at the point which shows the electroconductivity which is not influenced by humidity.
The crystalline metal oxide or composite oxide fine particles thereof preferably have a volume resistance of 10 ⁷ Ω · cm or less, and preferably 10 ⁵ Ω · cm or less. The particle size is preferably 0.01 μm to 0.7 μm, more preferably 0.02 μm to 0.5 μm.

The method for producing fine particles of the conductive crystalline metal oxide and its composite oxide is described in detail in JP-A-56-143430. For example, (1) firing metal oxide fine particles (2) A method of heat treatment in the presence of different atoms for improving conductivity, (2) A method of coexisting different atoms for improving conductivity when producing metal oxide fine particles by firing, (3) For example, a method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing metal oxide fine particles by firing is mentioned.
Examples of the hetero atoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sb, Nb, and halogen atoms for SnO ₂ .
The addition amount of the different atoms is preferably 0.01 mol% to 30 mol%, more preferably 0.1 mol% to 10 mol%. The amount of the conductive particles is ^{preferably 0.05g / m 2 ~20g / m 2} , 0.1g / m 2 ~10g / m 2 is more preferable.

In the conductive layer, as a binder, for example, cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate; vinylidene chloride, vinyl chloride, styrene, acrylonitrile, acetic acid Examples thereof include homopolymers or copolymers containing vinyl, alkyl (1 to 4 carbon atoms) acrylate, vinyl pyrrolidone and the like, soluble polyester, polycarbonate, soluble polyamide, and the like. In dispersing the conductive particles in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. Further, a binder crosslinking agent or the like may be added.
Examples of the titanium-based dispersant include titanate-based coupling agents and preneact (trade name: Ajinomoto Co., Ltd.) described in, for example, US Pat. No. 4,069,192 and US Pat. No. 4,080,353. Etc.).
Examples of the silane dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a “silane coupling agent”.
Examples of the binder crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent.
The conductive layer is provided by dispersing conductive fine particles in a binder and coating the temporary support, or by applying a subbing treatment to the temporary support and depositing the conductive fine particles thereon. Can do.

When the conductive layer is provided on the surface of the temporary support opposite to the light scattering layer, a hydrophobic polymer is provided on the conductive layer in order to improve scratch resistance. It is preferable to provide a hydrophobic polymer layer to be contained.
Examples of the hydrophobic polymer include vinyl polymers including cellulose esters (for example, nitrocellulose and cellulose acetate), vinyl chloride, vinylidene chloride, vinyl acrylate, and the like, polymers such as organic solvent-soluble polyamide and polyester.
The hydrophobic polymer layer may be applied in the form of a solution or aqueous latex dissolved in an organic solvent, and the coating amount is preferably about 0.05 g / m ² to ¹ g / m ^{2 in} terms of dry mass.
For the hydrophobic polymer layer, for example, an organic carboxylic acid amide as described in JP-A-55-79435 may be used as a slipping agent for imparting slipping property. There is no problem in adding a matting agent or the like.
Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer is not substantially affected. In the case of providing an undercoat layer, JP-A-51-135526, US Pat. No. 3,143,421, US Pat. No. 3,586,508, US Pat. No. 2,698,235 No. 1, US Pat. No. 3,567,452, etc., vinylidene chloride copolymer, Japanese Patent Application Laid-Open No. 51-114120, US Pat. No. 3,615,556 Diolephine-based copolymers such as butadiene as described in JP-A No. 51-58469, glycidyl acrylate or glycidyl methacrylate-containing copolymers as described in JP-A No. 48-24923 Polyamide-epichlorohydrin resin as described in JP-A No. 50-39536, and maleic anhydride-containing copolymer as described in JP-A-50-39536 Or the like can be used. Also, JP-A 56-82504, JP-A 56-143443, JP-A 57-104931, JP-A 57-118242, JP 58-62647, JP A conductive layer disclosed in JP-A-60-258541 can also be used as appropriate.

When the conductive layer is contained in a plastic raw material that is the same as or different from the base film, and the base film is coextruded at the same time, a conductive layer excellent in adhesion and scratch resistance can be easily obtained. be able to. In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, which is a particularly preferable embodiment of the conductive layer.
When the conductive layer is applied, usual methods such as roller coating, air knife coating, gravure coating, bar coating, and curtain coating can be employed.

In order to prevent electrostatic shock due to electrification using the light scattering layer transfer material, the surface electrical resistance value of the conductive layer or the support provided with conductivity is preferably 10 ¹³ Ω or less. More preferably, it is ¹² Ω or less. In order to improve the slipperiness or to prevent the light scattering layer from adversely adhering to the backside of the temporary support, a known fine particle-containing slipping composition or a release material containing a silicone compound is provided on the backside of the temporary support. It is also useful to apply a mold composition or the like.

  When a conductive layer is provided on the surface of the temporary support on which the thermoplastic resin layer is not provided, in order to increase the adhesive force between the thermoplastic resin layer and the temporary support, Surface treatment such as treatment, corona treatment, ultraviolet irradiation treatment, adding phenolic substances such as cresol novolac resin and resorcin to the thermoplastic resin layer, polyvinylidene chloride resin, styrene butadiene rubber, gelatin on the base material For example, an undercoating process can be performed, or a process combining these processes can be performed. Among these, when the thermoplastic resin is alkali-soluble, a polyethylene terephthalate film coated with gelatin after corona treatment is preferable because it provides particularly excellent adhesion. The thickness of the gelatin layer is preferably 0.01 μm to 2 μm.

  In addition, for the purpose of improving adhesion to the thermoplastic resin layer, these sheets are subjected to surface treatment such as glow discharge treatment, corona treatment, ultraviolet irradiation treatment, undercoating treatment such as polyvinylidene chloride resin, styrene butadiene rubber and gelatin. In addition, a phenolic substance such as cresol novolac resin or resorcin can be added to the thermoplastic resin layer, and further a combination of these treatments can be performed. Among these, a polyethylene terephthalate film subjected to gelatin undercoating is preferred in terms of excellent adhesion, and a polyethylene terephthalate film primed with gelatin after corona treatment is particularly preferred because it provides further excellent adhesion. The thickness of the gelatin layer is preferably 0.01 μm to 2 μm.

<Thermoplastic resin layer>
As the organic polymer substance used as the thermoplastic resin layer, an organic polymer having a softening point of about 80 ° C. or less by the Viker Vicat method (specifically, a method for measuring a softening point of a polymer by the American Material Testing Method ASTM D1235). It is preferable to be selected from substances. The reason for this is that by using a polymer with a low softening point, when transferring the light scattering layer transfer material onto an uneven substrate with heat and pressure, the underlying unevenness is completely absorbed, and there is no residual bubble. It is because it becomes possible to do. When a polymer having a high softening point is used, it is necessary to transfer at a high temperature, which is disadvantageous in actual work. From such a point, the organic polymer substance used for the thermoplastic resin layer preferably has a softening point by Vicat method of 80 ° C. or less, more preferably 60 ° C. or less, and further preferably 50 ° C. or less.
Examples of those having a softening point of 80 ° C. or less include polyolefins such as polyethylene and polypropylene; ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof; ethylene and acrylate esters or saponified products thereof; polyvinyl chloride; Vinyl chloride copolymer such as vinyl chloride and vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, Polyvinyltoluene, vinyltoluene and vinyltoluene copolymers such as (meth) acrylic acid esters or saponified products thereof, poly (meth) acrylic acid esters, (meth) acrylic acid esters such as (meth) acrylic acid butyl and vinyl acetate Copolymer, vinyl acetate copolymer nylon, copolymer If nylon, N- alkoxymethyl nylon, and organic polymers of the polyamide resin such as N- dimethylamino nylon and the like. Furthermore, use of organic polymers with a softening point of about 80 ° C or less according to "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) Can do.

  It is also possible to add various plasticizers compatible with the polymer material to these organic polymer materials to lower the substantial softening point. For example, an organic high polymer having a softening point of 80 ° C. or higher. Various plasticizers compatible with the polymer substance can be added to the molecular substance to lower the substantial softening point to 80 ° C. or lower.

  The solubility characteristics of these organic polymer substances may be sufficiently matched with the solubility characteristics of the light scattering layer, or may have solubility characteristics that are soluble in a solvent in which the light scattering layer does not dissolve at all. In addition, in order to adjust the adhesive force with the base material in these organic polymer substances, various polymers, supercooling substances, adhesion improvers, surfactants, release agents, and the like within a range where the substantial softening point does not exceed 80 ° C. It is possible to add molds and the like.

  The thickness of the thermoplastic resin layer is preferably 6 μm or more. This is because, if the thickness of the thermoplastic resin layer is 5 μm or less, it becomes impossible to completely absorb the unevenness of the foundation of 1 μm or more. The upper limit is not particularly limited in terms of performance, but is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of production suitability.

As the material for the thermoplastic resin layer, an alkali-soluble photopolymerizable resin is preferably used. There is no restriction | limiting in particular as this alkali-soluble photopolymerizable resin, According to the objective, it can select suitably, For example, (meth) acrylic acid and (meth) acrylic-acid alkylester (As an alkyl group, methyl group, ethyl Group, butyl group, etc.), poly (meth) acrylic acid, copolymer of styrene and unsaturated dibasic acid anhydride such as maleic anhydride, reaction product of the polymer and alcohol, cellulose And a reaction product with a polybasic acid anhydride.
Among the above polymers, styrene / maleic anhydride copolymer, methyl methacrylate / methacrylic acid / 2-ethylhexyl methacrylate / benzyl methacrylate quaternary copolymer described in JP-A-60-258539, JP-B-55. Styrene / maleic acid mono-n-butyl ester copolymer described in JP-A-38961, styrene / methyl methacrylate / ethyl acrylate / methacrylic acid quaternary copolymer described in JP-B-54-25957, Benzyl methacrylate / methacrylic acid copolymer described in JP-A-52-99810, acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid terpolymer described in JP-B-58-12577, JP-B 55-6210 Three of methyl methacrylate / ethyl acrylate / acrylic acid described in the publication Copolymer and isopropanol portion esterified styrene / maleic anhydride copolymer, etc. are preferable.

The thermoplastic resin needs to exhibit releasability with the separation layer. For this purpose, it is preferable to add a release agent into the alkali-soluble thermoplastic resin. As the mold release agent, a silicone compound or a fluorinated alkyl group-containing compound is suitable. Among these, as the silicone compound, Daicel UCB Co., Ltd. Evecryl 1360, Evekril 350; Toshiba Silicone Co., Ltd. dimethyl silicone oil TSF400, methylphenyl silicone oil TSF4300, silicone polyether copolymers TSF4445, TSF4446, TSF4460, TSF4452, etc. Is mentioned. Examples of the fluorinated alkyl group-containing compound include a fluorine-based surfactant and a fluorine-based graft polymer.
Examples of the fluorosurfactant include perfluoroalkyl group / hydrophilic group-containing oligomer F-171, perfluoroalkyl group / lipophilic group-containing oligomer F-173 manufactured by Dainippon Ink and Chemicals, Inc., perfluoroalkyl group. -Hydrophilic group / lipophilic group-containing oligomer F-177, perfluoroalkyl group / lipophilic group-containing urethane F-183, F-184. Examples of the fluorine-based graft polymer include Aron GF-300 and GF-150 manufactured by Toagosei Co., Ltd.

<Photothermal conversion layer>
When laser transfer is performed on the light scattering layer transfer material using a laser beam, it is preferable to provide a photothermal conversion layer between the temporary support and the thermoplastic resin layer.
The photothermal conversion layer contains a photothermal conversion material and a binder, and further contains other components as necessary.

  The photothermal conversion material is not particularly limited and can be appropriately selected depending on the purpose. For example, various carbon blacks such as acidic carbon black, basic carbon black, and neutral carbon black, and surface for improving dispersibility. Various modified or surface-coated carbon blacks, nigrosines, aniline black, cyanine black and other black pigments, phthalocyanine, naphthalocyanine green pigments, carbon graphite, aluminum, iron powder, diamine metal complexes, dithiol metal complexes, Phenolthiol metal complexes, mercaptophenol metal complexes, arylaluminum metal salts, inorganic water-containing inorganic compounds, copper sulfate, chromium sulfide, silicate compounds, titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, tungsten oxide Emissions, metal oxides such as indium tin oxide or the like, or hydroxides of these metals, sulfates, further bismuth, tin, tellurium, iron, aluminum metal powder, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from molybdenum, chromium, gold, silver, copper, aluminum, alloys thereof, and carbon black is particularly preferable.

  The binder is not particularly limited and may be appropriately selected from known binders that dissolve or disperse the photothermal conversion agent. For example, cellulose derivatives such as cellulose, nitrocellulose, and ethylcellulose; Of a styrene monomer such as a polymer or copolymer, a homopolymer or copolymer of a methacrylic ester such as polymethyl methacrylate or polybutyl methacrylate, an acrylic ester-methacrylic ester copolymer, polystyrene or α-methylstyrene Various synthetic rubbers such as homopolymers or copolymers, polyisoprene and styrene-butadiene copolymers; homopolymers of vinyl esters such as polyvinyl acetate; containing vinyl esters such as vinyl acetate-vinyl chloride copolymers Copolymer of polyurea, polyureta , Various polymers such as polyester and polycarbonate, “J. Imaging Sci., P59-64, 30 (2), (1986) (Frechet et al.)”, “Polymers in Electronics (Symposium Series, P11,242, T. Davidson, Ed. ACS Washington, DC (1984) (Ito, Willson)), “Microelectronic Engineering, P3-10, 13 (1991) (E. Reichmanis, L. F. Thompson)”, etc. And binders used in the "system".

  There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, surfactant, a solvent, various additives, etc. are mentioned.

  The thickness of the light-to-heat conversion layer is thicker than the thickness at which the laser light transmittance is almost zero (0), and is not affected by thermal diffusion, and is preferably 100 nm to 200 nm, particularly preferably about 100 nm.

<Separation layer>
The separation layer is not particularly limited as long as it is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. For example, JP-A 46-2121 and JP-B 56 -40824, polyvinyl ether / maleic anhydride polymer, water-soluble salt of carboxyalkyl cellulose, water-soluble cellulose ether, water-soluble salt of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, Various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various water-soluble salts of starch, or the like, styrene / maleic acid copolymers, maleate resins, etc. Is mentioned. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
The polyvinyl alcohol preferably has a saponification rate of 80% or more.
The content of the polyvinyl pyrrolidone is preferably 1% by mass to 75% by mass of the solid content of the separation layer. When the content is less than 1% by mass, sufficient adhesion with the light scattering layer cannot be obtained. When the content exceeds 75% by mass, the separation layer is formed when the light scattering layer coating liquid is applied on the separation layer. It may melt | dissolve and a separated layer may not be formed.
The thickness of the separation layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 2 μm. If the thickness is less than 0.1 μm, the oxygen permeability may be too high, and if it exceeds 5 μm, uneven coating may easily occur.

<Light scattering layer>
The light scattering layer contains a translucent resin and light scattering particles, and contains inorganic fine particles for adjusting the refractive index, and further contains other components as necessary.

-Translucent resin-
The translucent resin is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. Most of the layers using known photopolymerizable compositions have this property, but some layers can be further modified by the addition of a thermoplastic binder or a compatible plasticizer.

  As the translucent resin, there are three types of resins that are mainly cured by ultraviolet rays and electron beams, that is, an ionizing radiation curable resin, a mixture of an ionizing radiation curable resin and a thermoplastic resin and a solvent, and a thermosetting resin. used.

  The translucent resin is preferably a polymer having a saturated hydrocarbon or polyether as a main chain, and more preferably a polymer having a saturated hydrocarbon as a main chain. The translucent resin is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a cross-linked translucent resin, it is preferable to use a monomer having two or more ethylenically unsaturated groups.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, penta Erythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinyl base Zen derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfones (eg, divinyl sulfone), acrylamides (eg, methylenebisacrylamide) , Methacrylamide, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, an acrylate or methacrylate monomer having at least three functional groups, and further an acrylate monomer having at least five functional groups are preferable from the viewpoint of film hardness, that is, scratch resistance. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is commercially available and is particularly preferably used.

  These monomers having an ethylenically unsaturated group can be dissolved in a solvent together with various polymerization initiators and other additives, applied, dried, and then cured by a polymerization reaction by ionizing radiation or heat.

  Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced by reaction of a crosslinkable group. Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. In addition, vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester, urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A crosslinkable functional group may be used as a result of the decomposition reaction, such as a block isocyanate group. That is, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. These monomers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

  In addition to the monomer having two or more ethylenically unsaturated groups, a monomer having a high refractive index may be introduced. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenyl thioether, and the like. These may be used individually by 1 type and may use 2 or more types together.

Examples of the solvent include ethers having 3 to 12 carbon surfaces, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and organic solvents having two or more functional groups; methanol, Ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2 -Pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the ethers having 3 to 12 charcoal surfaces include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, and 1,3,5-trioxane. , Tetrahydrofuran, anisole, phenetole and the like. These may be used individually by 1 type and may use 2 or more types together.
Examples of the ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone. These may be used individually by 1 type and may use 2 or more types together.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, propion brewed ethyl, n-pentyl acetate, and γ-ptyrolactone. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the organic solvent having two or more kinds of functional groups include methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, Examples include 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate. These may be used individually by 1 type and may use 2 or more types together.

As a curing method of the ionizing radiation curable resin composition as described above, the ionizing radiation curable resin composition can be cured by a normal curing method, that is, irradiation with an electron beam or ultraviolet rays.
For example, in the case of electron beam curing, 50 keV to 1000 keV emitted from various electron beam accelerators such as a Cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type. Preferably, an electron beam having an energy of 100 keV to 300 keV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, etc. are used. it can.

-Light scattering particles-
The light scattering particles are not particularly limited, and may be organic fine particles or inorganic fine particles.
Examples of the organic fine particles include polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, polystyrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde beads.
Examples of the inorganic fine particles include SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , and Sb ₂ O ₃ .
The average particle diameter of the light scattering particles is preferably 50 nm to 300 nm, and more preferably 150 nm to 250 nm. If the average particle size is less than 50 nm, the particles hardly scatter light, so that the effect of improving the light extraction efficiency may not be obtained. If the average particle size exceeds 300 nm, the particle distribution is uneven on the scattering layer surface. Therefore, the transferability may be impaired due to the formation of gaps during transfer or the in-plane distribution of adhesion.
The average particle diameter of the light scattering 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.

-Inorganic fine particles-
In addition to the above materials, the light scattering layer may contain inorganic fine particles such as metal oxide ultrafine particles having a high refractive index.
As the metal oxide ultrafine particles having a high refractive index, fine particles having a particle diameter of 100 nm or less made of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony are contained. Preferably, it contains fine particles of 50 nm or less.
_{Specifically, ZrO 2, TiO 2, Al} 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, ITO , and the like. Among these, ZrO ₂ is particularly preferable. The addition amount of the high refractive index monomer and the metal oxide ultrafine particles is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass with respect to the total mass of the translucent resin. .

  In addition to the above materials, ultrafine particles having a low refractive index may be contained therein. The ultrafine particles having a low refractive index preferably contain silica fine particles having a particle size of 100 nm or less, preferably 50 nm or less. Moreover, you may use the hollow silica which contains air in particle | grains and expresses a lower refractive index. The addition amount of the ultrafine particles having a low refractive index is preferably 10% by mass to 90% by mass and more preferably 20% by mass to 80% by mass with respect to the total mass of the adhesive.

  The thickness of the light scattering layer is preferably 0.5 μm to 5 μm, and more preferably 0.75 μm to 3 μm. If the thickness is less than 0.5 μm, a sufficient amount of light scattering cannot be obtained, so that the effect of improving the light extraction efficiency may not be obtained. If the thickness exceeds 5 μm, peeling from the substrate may occur during transfer. In-plane distribution may occur in the state and uneven brightness may occur.

The light scattering layer contains (1) a high refractive index translucent resin having a refractive index of 1.6 or more and light scattering particles having a refractive index difference between the translucent resin of 0.05 or more. Aspects, (2) an aspect containing high-refractive-index light scattering particles having a refractive index of 2.0 or more, and the like are preferable.
Examples of the high refractive index translucent resin (1) having a refractive index of 1.6 or more include dipentaerythritol hexa (meth) acrylate containing ZrO ₂ fine particles.
Examples of the light scattering particles having a refractive index difference of 0.05 or more with respect to the translucent resin include SiO ₂ , ZrO ₂ , and TiO ₂ .
Examples of the high refractive index light scattering particles (2) having a refractive index of 2.0 or more include ZrO ₂ and TiO ₂ .

<Coating sheet>
A thin covering sheet is preferably provided on the light scattering layer in order to protect it from contamination and damage during storage.
The covering sheet may be made of the same or similar material as the temporary support, but it must be easily separated from the light scattering layer. As a covering sheet material, for example, a silicone paper, a polyolefin or a polytetrafluoroethylene sheet is preferable, and a polyethylene film or a polypropylene film is more preferable.
The thickness of the covering sheet is preferably 5 μm to 100 μm, and more preferably 10 μm to 30 μm.

<Method for producing light scattering layer transfer material>
The light scattering layer transfer material of the present invention is, for example, (1) When laser transfer is performed on a temporary support, a photothermal conversion layer coating solution is applied and dried to form a photothermal conversion layer, and the photothermal conversion layer A thermoplastic resin layer solution is applied on top and dried to provide a thermoplastic resin layer, and then a separation layer material solution consisting of a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer and dried. Thereafter, the light scattering layer is coated with a solvent that does not dissolve the separation layer and dried. (2) A light scattering layer is provided on another covering sheet, and the sheet having both the thermoplastic resin layer and the separation layer on the temporary support is mutually connected so that the separation layer and the light scattering layer are in contact with each other. Manufactured by bonding. (3) As another covering sheet, a temporary support having a thermoplastic resin layer is prepared, and this thermoplastic resin layer is bonded to the light scattering layer on the covering sheet and the separation layer of the sheet composed of the separation layer. Manufactured by.

In place of the temporary support provided with the thermoplastic resin layer by coating, a two-layer or multilayer sheet in which the thermoplastic resin sheet and the temporary support sheet are bonded can also be used.
As the thermoplastic resin sheet, the same material as the thermoplastic resin layer can be used, and among these, a polyethylene film or a polypropylene film is particularly preferable.
As a method of providing a polyethylene film or a polypropylene film on a temporary support, for example, (1) Applying a solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane, natural rubber, synthetic rubber or the like on the temporary support. (2) Ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, polyamide resin, petroleum A method in which a polyethylene film or a polypropylene film is laminated immediately after an adhesive made of a mixture of resin, rosin and wax is heated and melted and applied onto a substrate. (3) Extruded after melting polyethylene or polypropylene. Extruded into a film by a machine and remains in a molten state How to laminate by bonding the substrate, and the like.

<Transfer method>
The light scattering layer transfer method using the light scattering layer transfer material of the present invention will be described.
First, the cover sheet of the light scattering layer transfer material is removed, and the light scattering layer is bonded onto the transfer target under pressure and heating. Conventionally known laminators and vacuum laminators can be used for bonding, and an auto-cut laminator can also be used in order to increase productivity. Thereafter, the temporary support and the thermoplastic resin layer are peeled off to form a light scattering layer.
Here, as shown in FIG. 3, first, the cover sheet of the light scattering layer transfer material is peeled off, and the surface of the light scattering layer 12 is pressurized and heated using a laminator 14 on the barrier layer 11 of the organic EL display device. Then, the temporary support 13 is removed, and the light scattering layer 12 can be transferred onto the barrier layer 11 of the organic EL display device. In FIG. 3, the thermoplastic resin layer and the separation layer of the light scattering layer transfer material are omitted.

The light scattering layer transfer method using the light scattering layer transfer material for laser transfer of the present invention will be described.
First, the cover sheet of the light scattering layer transfer material is removed, and the light scattering layer is bonded onto the transfer target under pressure and heating. Conventionally known laminators and vacuum laminators can be used for bonding, and an auto-cut laminator can also be used in order to increase productivity. Then, the laser beam which focused on the position of the photothermal conversion layer of a laminated body is irradiated, a temporary support body and a thermoplastic resin layer are peeled, and a light-scattering layer is formed.
Since the laser light can be easily concentrated to increase the light intensity in a minute region, it is suitable for generating heat by irradiating the photothermal conversion material in the present invention with light. As the wavelength region of the laser used for irradiation, those in the ultraviolet to infrared region can be used, and as the laser method, both a continuous wave method and a pulse method can be used. As a laser medium, for example, a gas laser is used. Semiconductor lasers, ultraviolet excitation dye lasers, fiber amplifier lasers, and the like can be used.
The laser light can be uniformly transferred over the entire surface of the light scattering layer by scanning the transfer material using an XY stage or a polygon mirror. Further, it is possible to form a patterned light scattering layer by turning on and off the output of the laser beam while scanning.

  Here, as shown in FIG. 4, first, the cover sheet of the light scattering layer transfer material was peeled off, and the surface of the light scattering layer 12 was pressed and bonded to the barrier layer 11 of the organic EL display device using a laminator. . The laminated body was irradiated with a laser beam 16 focused on the position of the photothermal conversion layer 15, and the light scattering layer 12 was transferred onto the barrier layer 11 of the organic EL display device. Subsequently, the temporary support is removed, and a light scattering layer can be formed on the barrier layer of the organic EL display device. In FIG. 4, the thermoplastic resin layer and the separation layer of the light scattering layer transfer material are omitted.

  Since the light-scattering layer transfer material of the present invention does not contain water and solvent, the light-scattering layer can be efficiently formed without damaging the organic EL display device. Therefore, the organic EL display device described below It is suitable for production of a light scattering layer on the negative electrode (or barrier layer).

(Organic EL display device and organic EL display device manufacturing method)
The organic EL display device of the present invention has a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate, and is formed on the barrier layer using the light scattering layer transfer material of the present invention. May have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a barrier layer, etc., and each of these layers has other functions. It may be a thing. Various materials can be used for forming each layer.
The method for producing an organic EL display device of the present invention is a method for producing an organic EL display device having a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate,
In the first embodiment, the light scattering layer transfer material of the present invention is attached by a laminator so that the light scattering layer side surface is in contact with the barrier layer.
In the second embodiment, the light scattering layer transfer material of the present invention is attached so that the surface on the light scattering layer side is in contact with the barrier layer, and light is irradiated from the temporary support side to the position of the photothermal conversion layer.

-Positive electrode-
The positive electrode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. The material preferably has a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like.
There is no restriction | limiting in particular in the thickness of the said positive electrode, Although it can select suitably with materials, 10 nm-5 micrometers are preferable, 50 nm-1 micrometer are more preferable, 100 nm-500 nm are still more preferable.

As the positive electrode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica.
The thickness of the substrate is not particularly limited as long as it is sufficient to maintain mechanical strength, but when glass is used, it is preferably 0.2 mm or more, and more preferably 0.7 mm or more.

  A barrier film can also be used as the transparent resin substrate. The barrier film is a film in which a gas impermeable barrier layer is provided on a plastic support. As the barrier film, a film in which silicon oxide or aluminum oxide is vapor-deposited (Japanese Patent Publication No. 53-12953, Japanese Patent Laid-Open No. 58-217344), an organic-inorganic hybrid coating layer (Japanese Patent Laid-Open No. 2000-323273, JP-A-2004-25732), those having an inorganic layered compound (JP-A-2001-205743), laminates of inorganic materials (JP-A-2003-206361, JP-A-2006-263389), organic Layer and inorganic layer laminated alternately (Japanese Patent Laid-Open No. 2007-30387, US Pat. No. 6,436,645, Affinito et al., Thin Solid Films 1996, pages 290-291), an organic layer and an inorganic layer continuously A laminate (US Patent Application Publication No. 2004-46497) and the like can be mentioned.

  Various methods are used for producing the positive electrode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), a dispersion of indium tin oxide. A film is formed by a method such as application of an object. The positive electrode can be subjected to cleaning or other processing to lower the driving voltage of the display device or to increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment is effective.

-Negative electrode-
The negative electrode supplies electrons to an electron injection layer, an electron transport layer, a light emitting layer, and the like. Adhesion, ionization potential, stability between the negative electrode and an adjacent layer such as an electron injection layer, an electron transport layer, and a light emitting layer are stable. It is selected in consideration of sex and the like.
As the material of the negative electrode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples thereof include alkali metals (for example, Li, Na, K, etc.) or fluorides thereof. Alkaline earth metals (eg Mg, Ca, etc.) or fluorides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or mixed metals thereof, lithium-aluminum alloys or mixed metals thereof, magnesium-silver alloys or those thereof Or a rare earth metal such as indium and ytterbium. Among these, a material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy, or a mixed metal thereof is more preferable.
There is no restriction | limiting in particular in the thickness of the said negative electrode, Although it can select suitably with materials, 10 nm-5 micrometers are preferable, 50 nm-1 micrometer are more preferable, 100 nm-1 micrometer are still more preferable.
For the production of the negative electrode, for example, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a coating method or the like is used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a pre-adjusted alloy may be vapor-deposited.
The sheet resistance of the positive electrode and the negative electrode is preferably low, and is preferably several hundred Ω / □ or less.

  The barrier film may be bonded onto the negative electrode to prevent gas from entering, and a protective layer may be formed on the display surface.

-Light emitting layer-
The material of the light emitting layer has a function that can inject holes from the positive electrode or hole injection layer and hole transport layer when an electric field is applied, and can inject electrons from the negative electrode or electron injection layer and electron transport layer. Any layer can be used as long as it can form a layer having a function of transferring injected charges and a function of emitting light by providing a recombination field of holes and electrons. Examples of the light emitting layer material include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, Oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives Various metal complexes represented by metal complexes and rare earth complexes of polythiophene, polyphenylene, polyphenylene vinyle Polymeric compounds such as and the like.
There is no restriction | limiting in particular in the thickness of the said light emitting layer, According to the objective, it can select suitably, 1 nm-5 micrometers are preferable, 5 nm-1 micrometer are more preferable, 10 nm-500 nm are still more preferable.
The method for forming the light emitting layer is not particularly limited and may be appropriately selected depending on the purpose. For example, resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spin coating method, casting method, dip coating) Method) and LB method. Among these, resistance heating vapor deposition and a coating method are particularly preferable.

-Hole injection layer, hole transport layer-
The material of the hole injection layer and the hole transport layer has any one of the function of injecting holes from the positive electrode, the function of transporting holes, and the function of blocking electrons injected from the negative electrode. I just need it. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples thereof include conductive polymers such as copolymers, thiophene oligomers, and polythiophenes.
The thicknesses of the hole injection layer and the hole transport layer are not particularly limited and can be appropriately selected according to the purpose. For example, 1 nm to 5 μm is preferable, 5 nm to 1 μm is more preferable, and 10 nm to 500 nm is still more preferable. .
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.
As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection / transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating). Law). In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

-Electron injection layer, electron transport layer-
The material of the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the negative electrode, a function of transporting electrons, and a function of blocking holes injected from the positive electrode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Various metal complexes such as pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, metal complexes of phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole and benzothiazole as ligands, etc. Is mentioned.
The thicknesses of the electron injection layer and the electron transport layer are not particularly limited and may be appropriately selected depending on the purpose. The thickness is preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm.
The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
As a method for forming the electron injection layer and the electron transport layer, a vacuum deposition method, an LB method, a method in which the electron injection / transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method, etc.) Etc. are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

-Barrier layer-
The barrier layer is not particularly limited as long as it has a function of preventing permeation of oxygen, moisture, nitrogen oxides, sulfur oxides, ozone and the like in the atmosphere, and can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as a material of the said barrier layer, According to the objective, it can select suitably, For example, SiN, SiON, etc. are mentioned.
There is no restriction | limiting in particular as thickness of the said barrier layer, Although it can select suitably according to the objective, 5 nm-1,000 nm are preferable, 7 nm-750 nm are more preferable, 10 nm-500 nm are especially preferable. If the thickness of the barrier layer is less than 5 nm, the barrier function for preventing the permeation of oxygen and moisture in the air may be insufficient. If the thickness exceeds 1,000 nm, the light transmittance decreases and the transparency is reduced. May be damaged.
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.
There is no restriction | limiting in particular as a formation method of the said barrier layer, According to the objective, it can select suitably, For example, CVD method etc. are mentioned.

  Since the organic EL display device of the present invention has a light scattering layer formed by using the light scattering layer transfer material of the present invention, it is excellent in light extraction efficiency and high quality with little luminance unevenness.

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

(Production Example 1)
<Production of organic EL display device>
First, a TFT is formed on an insulating substrate through a buffer layer, and then an interlayer insulating film layer made of a SiN film is deposited on the entire surface, and then reaches a source region and a drain region using a normal photoetching process. Each contact hole was formed.

  Next, after depositing an Al / Ti / Al multilayer structure conductive layer on the entire surface, patterning is performed using a normal photoetching process, thereby forming a source electrode so as to extend also on the TFT portion, and a drain. An electrode was formed. Note that the source electrode branches off from the common source line into four branch lines.

  Next, a photosensitive resin is applied to the entire surface using a spin coating method to form an interlayer insulating film, and this interlayer insulating film is exposed using a predetermined mask, and then developed using a predetermined developer, whereby the source A contact hole for the branch line of the electrode was formed. For convenience, a contact hole is formed for the common source line.

  Next, an aluminum (Al) film is deposited on the entire surface by sputtering, and then patterned into a predetermined shape using a normal photoetching process, thereby connecting the divided positive electrode connected to the branch line of the source electrode through a contact hole Formed.

  Next, after forming an organic EL layer that covers the divided positive electrode exposed at the bottom of the pixel opening using a mask vapor deposition method, an Al film having a thickness of 10 nm that covers the organic EL layer again using a mask vapor deposition method, A common negative electrode is formed by sequentially depositing an ITO film having a thickness of 30 nm, and regions corresponding to the divided positive electrodes are divided pixel portions, respectively.

  In this case, the organic EL layer 130 includes, in order from the divided positive electrode side, a 2-TNATA (4,4 ′, 4 ″ -tris (2-naphthylphenylamino) triphenylamine) film and a hole transport layer as a hole injection layer. Α-NPD [N, N′-bis (1-naphthyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine] film as the light-emitting layer and Alq3 (8-quinolinol aluminum complex) ).

Next, a SiN film and a SION film were sequentially deposited on the entire surface by a CVD method to form a barrier layer having a thickness of 500 nm.
Next, a light scattering layer 170 was formed on the barrier layer according to Examples and Comparative Examples described later, and a glass plate 160 was attached as a transparent substrate on the light scattering layer.
As described above, an organic EL display device including the positive electrode 120 on the TFT substrate 110 illustrated in FIG. 2 and the organic EL layer 130, the negative electrode 140, the barrier layer 150, the light scattering layer 170, and the transparent substrate 160 in this order was manufactured.

(Preparation Example 1)
<Preparation of coating solution S1 for light scattering layer>
A light scattering layer coating solution S1 having the following formulation was prepared.
-Formulation of coating solution S1 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
Silica particles (KE-P10, particle size 0.1 μm, manufactured by Nippon Shokubai Co., Ltd.) ... 85 g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
In addition, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Preparation Example 2)
<Preparation of coating solution S2 for light scattering layer>
A light scattering layer coating solution S2 having the following formulation was prepared.
-Formulation of coating solution S2 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
・ Silica particle-containing liquid (Snowtex XL, average particle size 50 nm, solid concentration 40% by mass, manufactured by Nissan Chemical Industries, Ltd.) ... 210 g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
In addition, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Preparation Example 3)
<Preparation of coating solution S3 for light scattering layer>
A light scattering layer coating solution S3 having the following formulation was prepared.
-Formulation of coating solution S3 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
・ Silica particle-containing liquid (trade name: Oscar, average particle size 300 nm, solid content concentration 10% by mass, manufactured by Catalyst Chemical Industry Co., Ltd.) ... 850 g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
In addition, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Preparation Example 4)
<Preparation of coating solution S4 for light scattering layer>
A light scattering layer coating solution S4 having the following formulation was prepared.
-Formulation of coating solution S4 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
・ Silica particle-containing liquid (trade name “IPA-ST”, average particle size 400 nm, solid content concentration 33% by mass, manufactured by Nissan Chemical Industries, Ltd.) 255 g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
In addition, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Preparation Example 5)
<Preparation of coating solution S5 for light scattering layer>
A light scattering layer coating solution S5 having the following formulation was prepared.
-Formulation of coating solution S5 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
Silica particle-containing liquid (trade name: MEK-ST, average particle size 30 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Industries, Ltd.) 290 g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
Moreover, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Preparation Example 6)
<Preparation of coating solution S6 for light scattering layer>
A light scattering layer coating solution S6 having the following formulation was prepared.
-Formulation of coating solution S6 for light scattering layer-
・ Zirconia fine particle-containing hard coat composition liquid (Desolite Z7404, manufactured by JSR Corporation) ... 1000 g
・ UV curable resin (DPHA, Nippon Kayaku Co., Ltd.) ... 310g
・ Silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) ... 100g
Silica particles (KE-P10, particle size 0.1 μm, manufactured by Nippon Shokubai Co., Ltd.) ... 128g
・ Methyl ethyl ketone (MEK) ... 290g
・ Methyl isobutyl ketone (MIBK) ... 130g
In addition, the average particle diameter of the silica particle measured the number average particle diameter using the Nikkiso Co., Ltd nanotrac UPA-EX150.

(Comparative Example 1)
-Formation of light scattering layer-
The light scattering layer coating solution S1 was applied on the barrier layer of the organic EL display device of Production Example 1 so as to have a thickness of 3 μm.
First, after drying the solvent, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to cure the coating layer, A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 1)
<Preparation of Light Scattering Layer Transfer Material 1>
On a polyethylene terephthalate film substrate having a thickness of 100 μm, a coating liquid composed of the following thermoplastic resin layer formulation H1 was applied and dried to form a thermoplastic resin layer having a thickness of 20 μm.
-Formulation H1- of thermoplastic resin layer
・ Vinyl chloride / vinyl acetate copolymer (vinyl chloride / vinyl acetate (mass ratio) = 75/25, degree of polymerization: about 400, manufactured by Nissin Chemical Co., Ltd., MPR-TSL) ... 290.0 g
Vinyl chloride-vinyl acetate-maleic acid copolymer (vinyl chloride / vinyl acetate / maleic acid = 86/13/1 (mass ratio), degree of polymerization: about 400, manufactured by Nisshin Chemical Co., Ltd., MPR-TM)・ ・ 76.0g
・ Dibutyl phthalate: 88.5g
・ Fluorine surfactant (F-177P, manufactured by Dainippon Ink & Chemicals, Inc.) 5.4 g
・ Methyl ethyl ketone (MEK): 975.0 g

Next, a coating liquid comprising the following separation layer formulation B1 was applied onto the thermoplastic resin layer and dried to form a separation layer having a thickness of 1.6 μm.
-Separation layer formulation B1-
Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA205, saponification rate = 80%) ... 173.2 g
・ Fluorine surfactant ... 8g
・ Distilled water ... 2800g

Next, the light scattering layer coating liquid S1 is applied on the temporary support having the thermoplastic resin layer and the separation layer so as to have a thickness of 3 μm, and after drying the solvent, an air-cooled metal halide lamp of 160 W / cm. (Igraphics Co., Ltd.) was used to irradiate ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to cure the coating layer, thereby forming a light scattering layer. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

  Next, a 12 μm-thick polypropylene covering sheet was pressure-bonded onto the light scattering layer to produce a light scattering layer transfer material 1.

<Transfer>
The light scattering layer was transferred by the following method using the produced light scattering layer transfer material 1.
First, the cover sheet of the light scattering layer transfer material 1 is peeled off, and the light scattering layer surface is pressurized using a laminator (VP-II, manufactured by Taisei Laminator Co., Ltd.) on the barrier layer of the organic EL display device of Production Example 1. 0.8 kg / cm ² ), heating (130 ° C.) and bonding, followed by peeling at the interface between the separation layer and the thermoplastic resin layer, and simultaneously removing the substrate and the thermoplastic resin layer. A light scattering layer was formed on the barrier layer of the organic EL display device.

(Example 2)
-Production of light scattering layer transfer material 2 and production of organic EL display device-
A light scattering layer transfer material 2 was produced in the same manner as in Example 1 except that the light scattering layer coating liquid S1 was replaced with the light scattering layer coating liquid S2 in Example 1.
Using the produced light scattering layer transfer material 2, a light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 3)
-Production of light scattering layer transfer material 3 and production of organic EL display device-
A light scattering layer transfer material 3 was produced in the same manner as in Example 1 except that the light scattering layer coating liquid S1 was replaced with the light scattering layer coating liquid S3 in Example 1.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 3 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 2)
-Production of light scattering layer transfer material 4 and production of organic EL display device-
A light scattering layer transfer material 4 was produced in the same manner as in Example 1 except that the light scattering layer coating liquid S1 was replaced with the light scattering layer coating liquid S4 in Example 1.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 4 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 3)
-Production of light scattering layer transfer material 5 and production of organic EL display device-
A light scattering layer transfer material 5 was produced in the same manner as in Example 1 except that the light scattering layer coating liquid S1 was replaced with the light scattering layer coating liquid S5 in Example 1.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 5 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

Example 4
<Preparation of Light Scattering Layer Transfer Material 1 for Laser Transfer>
On the polyethylene terephthalate film base material, the composition H2 for photothermal conversion layer having the following formulation was applied so that the coating amount of carbon black after drying was 1.8 g / m ² to form a photothermal conversion layer.

-Photothermal conversion layer composition H2-
・ Carbon black ... 23g
・ Surfactant (Nissan Nonion NS208.5, manufactured by Nippon Oil & Fats Co., Ltd.) 5 mass% aqueous solution ... 27 g
・ 10% by weight aqueous solution of hydrophilic binder (gelatin) 350g
・ Polyethylene glycol (degree of polymerization 1,000) ... 12g
-Succinic acid-2-ethylhexyl ester sodium sulfonate 10 mass% solution (water / methanol = 1/1) ... 60 ml

  Next, a thermoplastic resin layer, a separation layer, a light scattering layer, and a cover sheet are formed on the produced light-to-heat conversion layer in the same manner as in Example 1, and the light scattering layer transfer material 1 for laser transfer is formed. Produced. The light scattering layer was formed using the light scattering layer coating liquid S1.

<Transfer>
Next, the light scattering layer was transferred by the following method using the light scattering layer transfer material 1 for laser transfer. First, the coating sheet of the light scattering layer transfer material 1 for laser transfer is peeled off, and the light scattering layer surface is laminated on the barrier layer of the organic EL display device of Production Example 1 using a laminator (manufactured by Taisei Laminator Co., Ltd., VP-II). Bonding was carried out under pressure (0.8 kg / cm ² ). The laminated body is irradiated with 830 nm laser light focused on the position of the photothermal conversion layer, and the light scattering layer is heated to a high temperature by the heat generated in the photothermal conversion layer. Was transferred onto the barrier layer. The laser beam was generated from a semiconductor laser LN9880 manufactured by Matsushita Electronics Co., Ltd. The spot diameter was 10 μm, and the organic EL display device mounted on the XY stage was scanned at a speed of 2 mm per second. The laser output was 60 mW. Then, it peeled in the interface of a separation layer and a thermoplastic resin layer, the temporary support body and the thermoplastic resin layer were removed simultaneously, and the light-scattering layer was formed on the barrier layer of the organic electroluminescence display of the manufacture example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 5)
-Production of light scattering layer transfer material 2 for laser transfer and production of organic EL display device-
In Example 4, the light-scattering layer transfer material 2 for laser transfer was produced in the same manner as in Example 4 except that the light-scattering layer coating solution S1 was replaced with the light-scattering layer coating solution S2.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1, using the produced light scattering layer transfer material for laser transfer 2 in the same manner as in Example 4. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 6)
-Production of light scattering layer transfer material 3 for laser transfer and production of organic EL display device-
In Example 4, the light-scattering layer transfer material 3 for laser transfer was produced in the same manner as in Example 4 except that the light-scattering layer coating solution S1 was replaced with the light-scattering layer coating solution S3.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 3 for laser transfer in the same manner as in Example 4. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 4)
-Production of light scattering layer transfer material 4 for laser transfer and production of organic EL display device-
In Example 4, the light-scattering layer transfer material 4 for laser transfer was produced in the same manner as in Example 1 except that the light-scattering layer coating liquid S1 was replaced with the light-scattering layer coating liquid S4.
Using the produced light scattering layer transfer material 4 for laser transfer, a light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 in the same manner as in Example 4. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 5)
-Production of light scattering layer transfer material 5 for laser transfer and production of organic EL display device-
In Example 4, the light-scattering layer transfer material 5 for laser transfer was produced in the same manner as in Example 4 except that the light-scattering layer coating solution S1 was replaced with the light-scattering layer coating solution S5.
Using the produced light scattering layer transfer material 5 for laser transfer, a light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 in the same manner as in Example 4. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 7)
-Production of light scattering layer transfer material 6 and production of organic EL display device-
In Example 1, a light scattering layer transfer material 6 was produced in the same manner as in Example 1 except that the thickness of the light scattering layer was changed from 3.0 μm to 0.5 μm.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 6 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Example 8)
-Production of light scattering layer transfer material 7 and production of organic EL display device-
A light scattering layer transfer material 7 was produced in the same manner as in Example 1 except that the thickness of the light scattering layer was changed from 3.0 μm to 5.0 μm in Example 1.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 7 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 6)
-Production of light scattering layer transfer material 8 and production of organic EL display device-
In Example 1, a light scattering layer transfer material 8 was produced in the same manner as in Example 1 except that the thickness of the light scattering layer was changed from 3.0 μm to 0.3 μm.
Using the produced light scattering layer transfer material 8, a light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 7)
-Production of light scattering layer transfer material 9 and production of organic EL display device-
A light scattering layer transfer material 9 was produced in the same manner as in Example 1 except that the thickness of the light scattering layer in Example 1 was changed from 3.0 μm to 7.0 μm.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 9 in the same manner as in Example 1. The volume filling factor of the light scattering particles in the obtained light scattering layer was 8%.

(Comparative Example 8)
-Production of light scattering layer transfer material 10 and production of organic EL display device-
A light scattering layer transfer material 10 was produced in the same manner as in Example 1 except that the light scattering layer coating liquid S1 was replaced with the light scattering layer coating liquid S6 in Example 1.
A light scattering layer was formed on the barrier layer of the organic EL display device of Production Example 1 using the produced light scattering layer transfer material 10 in the same manner as in Example 1. The volume filling factor of light scattering particles in the obtained light scattering layer was 12%.

  Next, regarding the organic EL display devices on which the light scattering layers of Examples 1 to 8 and Comparative Examples 1 to 8 were formed, luminance and luminance unevenness were evaluated as follows. The results are shown in Table 1.

<Evaluation of brightness>
Each organic EL display device was lit continuously under a constant current condition of 2.0 mA / cm ² , and front luminance was measured using a luminance meter (Topcon, BM5A).

<Evaluation of luminance unevenness>
The screen was equally divided into three parts, upper and lower, and left and right. From these nine points of average luminance Iave, maximum luminance Imax, and minimum luminance Imin, a luminance unevenness value was calculated from the following equation. A smaller value represents less luminance unevenness.
Brightness unevenness (%) = [(Imax−Imin) / Iave] × 100

  Since the light scattering layer transfer material of the present invention does not contain water and a solvent, the light scattering layer can be efficiently formed without damaging the organic EL display device. Therefore, it is suitable for manufacturing an organic EL display device with less content.

DESCRIPTION OF SYMBOLS 1 TFT substrate 2 Back electrode 3 Organic layer 4 Transparent electrode 5 Transparent substrate 11 Barrier layer 12 Light scattering layer 13 Temporary support 14 Laminator 15 Photothermal conversion layer 16 Laser light 110 Organic EL element 120 Positive electrode 130 Organic EL layer 140 Negative electrode 150 Barrier layer 160 Transparent substrate 170 Light scattering layer

Claims (8)

A light scattering layer transfer material for forming a light scattering layer on the negative electrode in an organic EL display device having at least a light emitting layer between a positive electrode and a negative electrode,
A temporary support, and at least a light scattering layer on the temporary support;
The light scattering layer contains at least a translucent resin and light scattering particles;
The light scattering layer transfer material, wherein the light scattering particles have an average particle diameter of 50 nm to 300 nm.   The light scattering layer transfer material according to claim 1, further comprising a photothermal conversion layer between the temporary support and the light scattering layer.   The light-scattering layer transfer material according to claim 2, wherein the light-heat conversion layer contains at least one light-heat conversion material selected from molybdenum, chromium, gold, silver, copper, aluminum, and alloys thereof, and carbon black. .   The light scattering layer transfer material according to claim 1, wherein the light scattering layer has a thickness of 0.5 μm to 5.0 μm.   The light scattering layer transfer material according to any one of claims 1 to 4, wherein a volume filling rate of light scattering particles in the light scattering layer is 10% or less. An organic EL display device having a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate,
An organic EL display device comprising a light scattering layer formed using the light scattering layer transfer material according to claim 1 on the barrier layer. A method for producing an organic EL display device having a positive electrode, an organic EL layer, a negative electrode, and a barrier layer in this order on a glass substrate,
6. A method for producing an organic EL display device, comprising attaching the light scattering layer transfer material according to claim 1 so that a surface on the light scattering layer side is in contact with the barrier layer by a laminator. A method for producing an organic EL display device having a positive electrode, an organic EL layer including at least a light emitting layer, a negative electrode, and a barrier layer in this order on a glass substrate,
The light scattering layer transfer material according to any one of claims 2 to 5 is attached so that the surface on the light scattering layer side is in contact with the barrier layer, and light is irradiated from the temporary support side to the position of the photothermal conversion layer. A method for manufacturing an organic EL display device.