JP2011146144A - Light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light emitting element having a base material and a protection member excellent in translucency, heat resistance, a passivation property (gas barrier property, oligomer delivery preventiveness, outgas reduction), water (moisture) absorption-proofness, chemical deterioration stability, dimensional state stability, surface anti-reflectiveness, an electric insulating property, ultraviolet deterioration resistance, and weatherability, and excellent in productivity to allow film formation under normal pressure or the like. <P>SOLUTION: This light emitting element includes a light transmissive lower electrode formed on the resin base material, a light emitting layer, and an upper electrode, and the light emitting element includes a layer comprising at least silicon oxynitride film between the light emitting layer and the resin base material. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a light emitting device having excellent gas barrier performance, and more particularly, to a light emitting device excellent in durability and flexibility.

The organic light emitting device is formed by depositing a hole transport material such as triphenyldiamine on a hole injection electrode such as tin-doped indium oxide (ITO) and further laminating a fluorescent material such as an aluminum quinolinol complex (Alq3) as a light emitting layer. Furthermore, it is an element having a basic configuration in which a metal electrode (electron injection electrode) having a small work function such as Mg is formed, and extremely high luminance of several hundreds to several 10,000 cd / m ² can be obtained at a voltage of about 10V.

  As a base material for such an organic light emitting element, a flexible material such as a flexible resin film is attracting attention in terms of application to a portable device. When a high heat-resistant film such as polyimide or aramid film is used as a base material having flexibility, these films are strong in hydrophilicity, so that the electrode material is caused by outgassing due to water absorption or moisture absorption of the film. The deterioration of the film quality of a thin film such as a light emitting film is a problem. In addition, curling, warping, and beveling of the thin film laminate including the base material are caused, and adverse effects are exerted on factors such as thermal shrinkage rate, linear expansion coefficient coefficient, and shape deformation.

  On the other hand, as a display using an organic light emitting element, application to a color display in which a ternary color of blue, green and red is obtained using a fluorescence conversion layer and / or a color filter layer made of a fluorescent material is being studied. (For example, see Patent Document 1).

  A method for forming a color display by combining a single light emitting layer with a fluorescent conversion layer and / or a color filter layer made of a fluorescent material can be composed of only a single organic light emitting element, so the structure is simple and inexpensive. In addition, it can be said that it is an excellent system in that it can be made full color by patterning the fluorescence conversion layer and / or the color filter layer.

  However, it is extremely difficult to provide the fluorescence conversion layer and / or the color filter layer in a predetermined pattern on the structure of the organic light emitting device from the viewpoint of patterning technology, damage to the organic light emitting structure, and the like. In addition, when a fluorescence conversion layer and / or a color filter layer is formed on a substrate and an organic light emitting structure is laminated thereon, a step is formed, so that a break (discontinuous portion of the film) occurs. Problems such as failure to function as an organic light-emitting device because the current cannot flow because the wiring is not connected, and the organic layers and electrodes are damaged by moisture and gas from these fluorescence conversion layers and / or color filter layers. The problem that it received and corroded occurred.

  As a means for solving such a problem, a method of further forming an overcoat layer on the fluorescence conversion layer and / or the color filter layer has been taken (for example, see Patent Document 2). The problem remains that the organic layer and the electrode are damaged or corroded.

  On the other hand, various studies such as formation of a passivation film have been made (see, for example, Patent Document 3), but the effect of preventing moisture and gas permeation of the film is insufficient, there is a problem in surface flatness, and during film formation. The above-mentioned conditions may cause damage to the fluorescent conversion layer and / or the color filter layer, the overcoat layer, and the like, which are the foundation, and are not practical.

  In addition, when a passivation film is formed particularly by a vacuum process, a method of increasing the thickness of the passivation film is conceivable in order to overcome the above problems. However, a thick passivation film takes a long time to manufacture, has poor productivity, and a film manufactured by a dry process has a large internal stress, resulting in cracks in the obtained passivation film. There was a problem that the effect could not be exhibited.

JP 2003-206361 A JP-A-8-236274 JP 2005-26193 A

  The objectives of the present invention are translucency, heat resistance, passivation (gas barrier properties, oligomer discharge prevention, outgas reduction), water absorption (humidity) resistance, chemical deterioration stability, dimensional shape stability, surface antireflection, It is to provide a light-emitting element having a substrate and a protective member that are excellent in productivity, such as being excellent in electrical insulation, UV light resistance, and in weather resistance, and capable of film formation under normal pressure. It is an object of the present invention to provide a light-emitting element having high performance, easy manufacturing, and low cost.

  The above object of the present invention can be achieved by the following configuration.

  1. A light-emitting element having a light-transmitting lower electrode formed on a resin substrate, a light-emitting layer, and an upper electrode, and comprising at least a silicon oxynitride film between the light-emitting layer and the resin substrate A light-emitting element having a layer.

  2. 2. The light emitting device according to 1 above, wherein the silicon oxynitride film is a layer formed of a silicon oxynitride film obtained by applying at least polysilazane between the light emitting layer and the resin base material and oxidizing the same. element.

  3. When the silicon oxynitride film has two or more layers, the element concentration ratio O / (O + N) of the silicon oxynitride film closest to the resin base material is the element concentration ratio O / (O + N) of the upper silicon oxynitride film. 3. The light emitting device according to 1 or 2 above, wherein the light emitting device is smaller.

  4). 4. The light-emitting element according to any one of 1 to 3, wherein the silicon oxynitride film is oxidized with ultraviolet light of 120 to 300 nm.

  According to the present invention, translucency, heat resistance, passivation properties (gas barrier properties, oligomer discharge prevention properties, outgas reduction), water absorption (humidity) resistance, chemical deterioration stability, dimensional shape stability, surface antireflection properties, Providing a light-emitting element having a substrate and a protective member with excellent productivity, such as electrical insulation, ultraviolet light degradation resistance, and thus excellent weather resistance, and capable of film formation under normal pressure, and has high reliability, A light-emitting element that is easy to manufacture and low in cost can be provided.

It is the cross-sectional schematic block diagram which showed the basic composition of the organic light emitting element which is a light emitting element of this invention.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  Compared to a silicon oxide film, a silicon oxynitride film can exhibit high gas barrier properties by containing nitrogen. However, when the nitrogen content increases and becomes nitrogen rich, coloring and the film itself become brittle. It is desirable to produce a silicon oxynitride film that balances this.

The light-emitting element of the present invention has a silicon nitride oxide layer on at least one surface of a substrate, and the formation method is realized by means such as vacuum deposition, ion plating, CVD, sputtering. In particular, sputtering that can form a dense film with good controllability of the composition, normal pressure for depositing an inorganic film by using discharge plasma treatment near atmospheric pressure, which does not require a vacuum process and is inexpensive to form. CVD is preferred. Sputtering includes an RF sputtering method using a Si ₃ N ₄ target as a raw material and a DC sputtering method in which Ar, O ₂ , and N ₂ gases are introduced using a Si target. When a Si target is used, an RF sputtering method can also be selected. More preferably, a coating solution in which polysilazane such as perhydropolysilazane is dissolved in, for example, xylene is applied, and then oxidized, that is, steam-oxidized, or separately or simultaneously with or after that, heat treatment in air or ultraviolet light irradiation is performed. Thus obtained silicon oxynitride film is obtained. The substrate is made of a material such as a resin having flexibility, translucency and heat resistance, and exists as a protective member (for example, a protective film) of a coating body such as various electronic devices. For example, like a board | substrate, you may exist as the structural member.

  For example, when a silicon oxynitride film as described above is provided on a resin base material, the heat resistance is improved, the surface flatness is improved, and the translucency is maintained while maintaining the flexibility of the resin. Many properties can be improved, such as improvements, substrate passivation, water absorption (humidity) resistance, chemical deterioration, dimensional stability, UV light resistance, and surface reflection reduction. . In addition, as a combined action of these, it is possible to impart long life and weather resistance. That is, since the water vapor and oxygen permeability is extremely low, in the light emitting element, performance deterioration due to them can be prevented and the life can be extended. Further, since a dense film can be obtained, the strength is improved and the corrosion resistance is excellent. Further, since a flat film can be obtained, the optical function of the electronic device such as a light emitting element is not reduced as well as the light transmitting property.

  In addition, the functional film formed on the base material or the base material, for example, an optical functional film such as a filter, and a functional thin film such as an electrode layer or a light emitting layer formed thereon can be passivated. These element constituent layers can be protected from moisture, gas, etc. released from the functional film formed on the material or the base material.

  Such a silicon oxynitride film is obtained by applying a polysilazane-containing coating solution such as perhydropolysilazane, and performing steam oxidation, oxidation by ultraviolet light irradiation, and / or heat treatment (including drying treatment). . This manufacturing method is a suitable method that enables a silicon oxynitride film to be formed on a resin base material having generally low heat resistance under normal pressure by a process technology with good productivity such as wet coating.

In the present invention, by laminating a silicon oxynitride layer (upper layer) and a silicon nitride oxide layer (lower layer) in this order on a resin substrate, not only the individual layers of the silicon nitride oxide layer upper layer and the silicon nitride oxide layer lower layer can be eliminated. It is a film that has a high water vapor barrier property and has high transparency as compared with the case where a defective portion of a non-layered structure is filled to form only individual layers. Furthermore, by making the lower layer of silicon nitride oxide layer a denser nitrogen-rich film than the upper silicon nitride oxide layer, it is possible to suppress outgas from the resin base material and organic layer during film formation, which is good A high-quality film having excellent transparency and water vapor barrier properties can be obtained. The composition of each silicon nitride oxide layer is not particularly limited. However, the upper layer of the silicon nitride oxide layer has an element concentration ratio of 0 <O / (O + N) ≦ 0.4, and the lower layer of the silicon nitride oxide layer has an element concentration ratio of 0.3 ≦ O. / (O + N) <1 is preferred. The thickness of each layer is not particularly limited, but the upper layer of the silicon nitride oxide layer preferably has a thickness of 1 to 50 nm, and the lower layer of the silicon nitride oxide layer preferably has a thickness of 10 to 500 nm. Within these ranges, good light transmittance and water vapor barrier properties can be obtained. About the formation method of a silicon oxynitride layer, it implement | achieves by means, such as vacuum evaporation, ion plating, CVD, sputtering. In particular, sputtering that can form a dense film with good controllability of the composition, normal pressure for depositing an inorganic film by using discharge plasma treatment near atmospheric pressure, which does not require a vacuum process and is inexpensive to form. CVD is preferred. Sputtering includes an RF sputtering method using a Si ₃ N ₄ target as a raw material and a DC sputtering method in which Ar, O ₂ , and N ₂ gases are introduced using a Si target. When a Si target is used, an RF sputtering method can also be selected.

  The silicon oxynitride film of the present invention may have a base layer in order to improve adhesion to a substrate, a fluorescent conversion layer containing a fluorescent substance, a color filter layer, a coating layer, and the like.

<Polysilazane>
The polysilazane that can be used in the present invention is a polymer having a silicon-nitrogen bond, as shown below, and is composed of Si ₂ , Si ₃ N ₄ , and both of Si—N, Si—H, N—H, and the like. Ceramic precursor inorganic polymer such as intermediate solid solution SiO _x N _y . Usually, perhydropolysilazane whose side chains are all hydrogen is used. Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight.

  These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As the organic solvent, it is not preferable to use an alcohol that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specifically, hydrocarbons such as pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, methylene chloride, chloroform Halogenated hydrocarbons such as carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, tetrachloroethane, ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran, tetrahydropyran, etc. is there.

  When these solvents are used, they may be selected to adjust the solubility of polysilazane, the evaporation rate of the solvent, and the increase in the concentration of the solution, and a plurality of types of solvents may be mixed according to the purpose.

  The content of polysilazane in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the thickness of the target silica film and the pot life of the coating solution.

  The organic polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, especially a methyl group having the smallest molecular weight, the adhesion to the base material is improved, and the hard and brittle silica film can be toughened. Occurrence is suppressed. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and in particular, there is little reduction in the original advantages of silica, such as improvement in amorphous silica purity and passivation after silica conversion, generation of heat outgas, and thermal expansion. In view of this, those having 1 carbon atom are preferred. However, a tertiary butyl group having 4 carbon atoms can be used to increase the viscosity of the non-aqueous solution or increase the thickness of the silica film depending on the coating conditions.

  When the polysilazane has the following structural formula, it is preferable that 20% or less of hydrogen atoms in the structural unit are substituted with an alkyl group, particularly a methyl group, particularly 10% or less. Furthermore, about 0.5 to 10% is preferable.

In the formula, R ¹ , R ² and R ³ represent an alkyl group. However, at least one of R ¹ , R ² and R ³ is a hydrogen atom.

Moreover, you may contain the photoinitiator as needed. By containing a photopolymerization initiator, particularly when the alkyl group part of the first layer of the base is a reactive double bond such as an alkylene group, the silica formation reaction is promoted and a denser silica film is obtained. In particular, the performance as a base film for forming the second layer is enhanced. Perhydropolysilazane promotes the formation of a composite of a micro inorganic filler (SiO ₂ ) and an organic polymer by introducing the organic silazane within a range that does not impair the original characteristics of the inorganic polymer. It contributes to "thickening", "stability improvement", "thickness limit improvement", and "flatness improvement", and promotes alloying due to high compatibility with acrylic resin, etc. It is confirmed that they are compatible with each other.

  As the photopolymerization initiator, known to well-known ones can be used. A commercially available product that is readily available is particularly preferred. A plurality of photopolymerization initiators may be used. Examples of the photopolymerization initiator include aryl ketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, α-acylose). Oxime esters), sulfur-containing photopolymerization initiators (for example, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. In particular, the use of an acylphosphine oxide photopolymerization initiator is preferred. Moreover, a photoinitiator can also be used in combination with photosensitizers, such as amines. Specific examples of the photopolymerization initiator include the following compounds.

  4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one.

  Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3, 3 'Dimethyl-4-methoxybenzophenone, 3,3', 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 ″ diethyl isophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

  4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4 -Diisopropylthioxanthone. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

  The photopolymerization initiator contributes little to the silica conversion of the inorganic polysilazane, and if it is too much, the denseness of the converted silica film is impaired. Therefore, it is preferable to contain about 0.01-5 mass% in an application liquid, and 20 mass% or less with respect to 100 mass parts of UV curable resin components in organic polysilazane.

  Moreover, you may use a catalyst in order to accelerate | stimulate reaction as needed. As the catalyst, a catalyst capable of curing polysilazane at a lower temperature is preferable. For example, metal catalysts composed of fine particles of metal such as gold, silver, palladium, platinum, nickel (Japanese Patent Laid-Open No. 7-196986), and their carboxyls. An acid complex (JP-A-5-93275) can be mentioned. Further, instead of adding the catalyst to the polysilazane solution, as proposed in Japanese Patent Laid-Open No. 9-31333, the catalyst is directly brought into contact with the catalyst solution, specifically an aqueous amine solution, or the like, or It is also preferable to employ a method such as exposing to the vapor for a certain period of time.

  As described above, polysilazane is a ceramic precursor polymer, and in order to form a silica film using this, it requires 450 ° C. or higher by atmospheric firing. By combining oxidation and / or heat oxidation in an air atmosphere, a dense silica film can be obtained even at 100 ° C. or lower, and can be formed on a substrate having low heat resistance such as a plastic film. In particular, a methyl group-substituted polysilazane capable of increasing the limit film thickness where cracks occur is particularly effective in the silica conversion efficiency by humidification. Therefore, any method of heating, steam oxidation, or a combination of heating, steam oxidation and heating in an air atmosphere may be used for forming the silica film. In particular, a polysilazane coating solution (Mn100 to 50000 of polysilazane) is vapor-phase contacted at 25 ° C. for 2 minutes in a vapor (non-phase) of a 5% by weight aqueous solution of trimethylamine as a catalyst, and then kept at 95 ° C. and 80% RH atmosphere for 5 minutes. A siliceous ceramic is formed. This method makes it possible to form a ceramic silica layer by continuous coating and curing on the plastic long film or the like.

Further, for example, the glycidol / polysilazane atomic ratio obtained by heating reaction of polysilazane of Mn 100 to 50000 and acetylacetonato complex (Ni, Pt, Pd, Al, Rh, etc.) is in the range of 1.0 × 10 ⁻⁶ to 2 In addition, the above-mentioned complex-added polysilazane fluid having a Mn of about 200 to 500,000 is calcined at a low temperature at 50 to 350 ° C., and a metal (Ag, Au, Pd, Ni, etc.) of 0.5 μm or less is added to the polysilazane having a Mn of 100 to 50,000. A silica ceramic film is obtained by low-temperature firing at 150 to 370 ° C. In this case, when baking is performed at 250 ° C. or higher in an atmosphere containing N ₂ or NH _{3, the} SiO _x N layer or a film close to the SiN _y layer (SiO _x) is slightly shifted from the partially silicon nitride stoichiometric composition. _Ny : O / (O + N) is converted to about 50 to 80%), and the passivation property is improved even in a thin layer.

  The means for applying the polysilazane-containing liquid is not particularly limited, and known to known methods can be employed. For example, dipping method, flow coating method, spray method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, spin coating method, slit coating method, micro gravure coating method, etc. are adopted. it can. After coating, if the coating composition contains a solvent, it is dried to remove the solvent. For the organic polysilazane-containing system, it is then cured by irradiating with ultraviolet rays or the like, if necessary, heated or left at room temperature. Harden. Curing can be accelerated by contacting with an aqueous solution or steam of amines or acids.

  In particular, in an organic polysilazane containing an acrylic resin having an ethylenically unsaturated double bond, active energy rays such as ultraviolet rays and electron beams may be irradiated when forming a silica film. In particular, when the photopolymerization initiator is contained in the coating film, it is necessary to irradiate light having a wavelength necessary for exciting the photopolymerization initiator, for example, UV light. Moreover, even when it does not contain a photopolymerization initiator, the reaction is accelerated by irradiating an electron beam, and a dense silica film hybridized with an organic polymer is easily obtained.

(Laminated)
As a more preferable form, the silicon oxynitride layer (upper layer) and the silicon nitride oxide layer (lower layer) are laminated in this order on the resin base material, so that it is not only the individual layers of the silicon nitride oxide layer upper layer and the silicon nitride oxide layer lower layer. It is a film that has a high water vapor barrier property and has high transparency as compared with the case where a defective portion of a non-layered structure is filled to form only individual layers. Furthermore, by making the lower layer of silicon nitride oxide layer a denser nitrogen-rich film than the upper silicon nitride oxide layer, it is possible to suppress outgas from the resin base material and organic layer during film formation, which is good A high-quality film having excellent transparency and water vapor barrier properties can be obtained. The composition of each silicon nitride oxide layer is not particularly limited. However, the upper layer of the silicon nitride oxide layer has an element concentration ratio of 0 <O / (O + N) ≦ 0.4, and the lower layer of the silicon nitride oxide layer has an element concentration ratio of 0.3 ≦ O. / (O + N) <1 is preferred. The thickness of each layer is not particularly limited, but the upper layer of the silicon nitride oxide layer preferably has a thickness of 1 to 50 nm, and the lower layer of the silicon nitride oxide layer preferably has a thickness of 10 to 500 nm. Within these ranges, good light transmittance and water vapor barrier properties can be obtained. About the formation method of a silicon oxynitride layer, it implement | achieves by means, such as vacuum evaporation, ion plating, CVD, sputtering. In particular, sputtering that can form a dense film with good controllability of the composition, normal pressure for depositing an inorganic film by using discharge plasma treatment near atmospheric pressure, which does not require a vacuum process and is inexpensive to form. CVD is preferred. Sputtering includes an RF sputtering method using a Si ₃ N ₄ target as a raw material and a DC sputtering method in which Ar, O ₂ , and N ₂ gases are introduced using a Si target. When a Si target is used, an RF sputtering method can also be selected.

  The silicon oxynitride film of the present invention may have a base layer in order to improve adhesion to a substrate, a fluorescent conversion layer containing a fluorescent substance, a color filter layer, a coating layer, and the like.

  The active energy ray for curing polysilazane is preferably ultraviolet rays. More preferred is UV light having a wavelength of 300 nm or less. However, it is not limited to ultraviolet rays, and an electron beam or other active energy rays can be used. As an ultraviolet ray source, a xenon lamp, a pulse xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or the like can be used.

<Base material>
As the substrate used in the present invention, a flexible substrate is preferable, and a resin material is particularly preferable. In particular, a resin base material having translucency and heat resistance at a glass transition point Tg of 65 ° C. or higher and / or a heat resistant temperature of 70 ° C. or higher is preferable.

  As a resin-made base material having translucency and heat resistance, polyethylene terephthalate film (Tg 79 ° C.), polyethylene naphthalate heat-resistant film (Tg 119 ° C.); ethylene trifluoride chloride resin [PCTFE: NEOFLON CTFE (manufactured by Daikin Industries, Ltd.) )] (Heat resistant temperature 150 ° C.), polyvinylidene fluoride [PVDF: Denka DX film (manufactured by Denki Kagaku Kogyo)]] (heat resistant temperature 150 ° C .: Tg 50 ° C.), polyvinyl fluoride (PVF: Tedlar PVF film (manufactured by DuPont) )] (Heat resistant temperature 100 ° C.) and other homopolymers, and tetrafluoroethylene-perfluorovinyl ether copolymer [PFA: neoflon: PFA film (manufactured by Daikin Industries) (heat resistant temperature 260 ° C.), tetrafluoroethylene- Hexafluoropropylene copolymer [FEP: Toyoflon Film FEP type (Toray Industries, Inc.)] (heat-resistant temperature 200 ° C.), tetrafluoroethylene-ethylene copolymer [ETFE: Tefzel ETFE film (DuPont) (heat-resistant temperature 150 ° C.), AFLEX film (Asahi Glass Co., Ltd .: Fluorine film such as copolymer such as Tg83 ° C.]; copolymerized aromatic polyester with divalent phenol such as aromatic dicarboxylic acid (for example, terephthalic acid / isophthalic acid) -bisphenol-A [PAR: casting Chemical Co., Ltd.) Elmec, heat-resistant temperature 290 ° C .: Tg 215 ° C.], [new PAR “MF series” (manufactured by Unitika), MF-2000, Tg 288 ° C.], etc .; polysulfone [PSF: Sumilite FS-1200 ( Manufactured by Sumitomo Bakelite Co., Ltd.)] (Tg 190 ° C), polyethersulfur (PES: Sumilite FS-5300 (Sumitomo Bakelite)) (Tg 223 ° C.) and other sulfur-containing polymer films; polycarbonate film [PC: Panlite (manufactured by Teijin Chemicals Ltd.)] (Tg 150 ° C.), [ITO film, buffer film, Laminated composite heat resistant PC film (manufactured by Teijin Ltd.) HT-60, Tg 205 ° C.]; amorphous polyolefin resin [APO (manufactured by Mitsui Chemicals), cycloolefin resin; ZEONOR: Nippon Zeon Co., Ltd. (Tg: 105- 163 ° C.)], functional norbornene resin [ARTON (Nippon Synthetic Rubber)] (heat-resistant temperature 164 ° C .: Tg 171 ° C.), polycyclohexene (PCHE: manufactured by Asahi Kasei) Tg 218 ° C .; polymethacrylate resin (PMMA) (manufactured by Mitsubishi Rayon) Yagumi Sumitomo Chemical Co., Ltd .: Tg 80-114 ° C); Olefin-maleimi Copolymer [TI-160 (manufactured by Tosoh Corporation)] (Tg 150 ° C. or higher), para-aramid (Aramika R: Asahi Kasei) (heat resistant temperature 200 ° C.), fluorinated polyimide (heat resistant temperature 200 ° C. or higher), polystyrene (Tg 90 ° C.) , Polyvinyl chloride (Tg 70 to 80 ° C.), cellulose triacetate (Tg 107 ° C.) and the like.

  Also, a composite film for LCD (Teijin Limited: Eleclear, HT-60), etc., with a polycarbonate film coated on both upper and lower sides with a gas barrier solvent-resistant layer and further provided with an ITO conductive film on one side, is a base film. Can be used as

  The glass transition point Tg of the resin substrate is 65 ° C. or higher, preferably 70 ° C. or higher, more preferably 180 ° C. or higher, particularly 230 ° C. or higher, and the upper limit is not particularly restricted, but is usually 350 ° C., particularly 300 ° C. Furthermore, it is about 250 degreeC. Further, the heat-resistant temperature or the continuous use temperature is 80 ° C. or higher, preferably 160 ° C. or higher, particularly 200 ° C. or higher. The upper limit is preferably as high as possible and is not particularly restricted, but is usually about 250 ° C. However, the device can be used as a package protective member (for example, a resin base material for a laminate film) at 80 ° C. or higher. The thickness of the resin substrate is appropriately determined depending on the purpose / use, required strength, bending rigidity, etc., but when used as a protective member, it is usually in the range of 5 to 150 μm, preferably 35 to 135 μm. In general, when the resin substrate is thinned, it is difficult to obtain the effect of surface protection. On the contrary, when the resin substrate is thickened to about 500 to 1000 μm, the flexibility and light transmittance generally tend to be lowered. For example, PES (Sumitomo Bakelite optical grade, smoothed FS-1300 series) has a thickness of 50 μm and a visible light transmittance of approximately 90%. The light transmittance can be sufficiently used.

  Note that having a light-transmitting property means that 60%, preferably 70%, more preferably 80% or more of light in the visible light region (particularly the light emission wavelength region of the element) is transmitted.

  Examples of organic-inorganic hybrid resin layers connected by covalent bonds include the following.

(1) Add 10 g of urethane acrylate (containing 15 acryloyl groups on average per molecule) and 15 g of xylene solution of perhydropolysilazane (solid content 20 mass%, number average molecular weight Mn≈1000), and stir at room temperature for about 1 hour (Wherein urethane acrylate is 2,4,6-trimethylbenzoyldiphenylphosphine oxide: 150 mg as photopolymerization initiator, and 2-hydroxy-5- (2-acryloyloxyethyl) phenylbenzotriazole as UV absorber) : 1000 mg, as a light stabilizer, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebanate: a solution obtained by dissolving 200 mg in butyl acetate: 30 g) with a doctor blade or the like Apply several μm, dry the solvent, use a high-pressure mercury lamp, 000mJ / cm ^2, wavelength: transparent cured product obtained by UV irradiation in an air atmosphere at 300～390Nm.

(2) In the UV / EB curable resin (Z series) system for optical parts manufactured by JSR Corporation, in particular, it is sensitive to SiO ₂ particles having a smaller particle diameter of 0.01 μm (10 nm) as compared with the visible light wavelength. Spin-coating organic solvent-containing types of organic / inorganic hybrid materials such as Desolite Z7500 series (Z7501, Z7503, KZ71714) into which a functional acryloyl group was introduced, drying the coating film, and then UV curing at 1.0 J / cm ² Resin layer.

  (3) Polysilsesquioxane modified with zirconia (trade name: ZRS, partially Zr substituted, ladder having R- and RO- groups on the side chain of the ring structure of the SiO skeleton, manufactured by Catalyst Chemical Industry Co., Ltd. Thermosetting organic-inorganic hybrid resin of structurally similar polymer).

  Furthermore, after forming any one of the underlayers (1), (2) and (3), the underlayer is made more siliceous by performing oxygen plasma treatment, and an upper polysilazane conversion layer is formed. In this case, the coverage due to the improved affinity between the two interfaces is also improved, and the effect of improving the passivation of the underlayer is added.

As the resin layer highly filled with ultrafine particles, UV / EB curing having an acrylic double bond in the resin material, organic peroxide thermosetting resin, epoxy ring-opening polymerization thermosetting resin, aluminum chelate compound Condensation transparent polyurethane resin of co-condensation resin with alkoxysilyl group-containing acrylic resin as condensation reaction catalyst, non-yellowing isocyanate group-containing urethane polymer, hydroxy acrylate resin, polyester, polyether (system hydroxyl group-containing polyol) prepolymer, etc. Those using one or more of these are preferred. The electrode particles are highly filled to the _resin, there may be mentioned _{SiO 2, Al 2 O 3,} ZrO 2, Ce 2 O 3, SiO, SiO x N y, the _Si 3 _{N 4,} or the like, in particular SiO ₂ Fine particles, SiO _x N _y fine particles, and the like are preferable. The average primary particle size of the ultrafine particles is preferably about 0.005 to 1.0 μm.

  The film thickness of these underlayers is preferably about 0.05 to 10 μm.

  By forming the silica film of the present invention directly on a color filter layer, a fluorescence conversion layer or the like without using an overcoat layer, good flatness can be obtained. In this case, as the surface roughness obtained, Rmax is within 30 nm.

  Further, the transmittance of the emitted light of the silica film is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. When the transmittance is low, the light emission itself from the light emitting layer is attenuated, and the luminance necessary for the light emitting element tends not to be obtained.

  In addition, when inorganic ultraviolet-absorbing fine particles (preferably zinc oxide (ZnO) fine particles) are contained in the silica film, these are added to the coating solution. The size of the fine particles is preferably 0.01 to 0.5 μm as an average particle size, and preferably contains about 25 to 35 vol% of polysilazane.

  Unlike inorganic semiconductor particles such as CdS, ZnO is non-polluting and stable in each environment as compared with organic materials. In addition, some are preferable as an organic ultraviolet absorber, and as such a polymer, a combination of a reactive ultraviolet absorber and a polymer is preferable.

[Organic light emitting device]
A preferred organic light emitting structure as the light emitting element structure is usually a hole injection electrode (positive electrode) such as ITO as the first electrode, an organic layer such as a hole injection transport layer, a light emitting layer, an electron injection transport layer, and the like. An electron injection electrode (cathode) is sequentially stacked. Moreover, you may have a color filter layer, a fluorescence conversion layer, and an overcoat layer as the foundation | substrate.

  The color filter layer may be a color filter used in a liquid crystal display or the like, but if the characteristics of the color filter are adjusted according to the light emitted from the organic light emitting device to optimize the extraction efficiency and color purity. Good. The light to be cut at this time is light having a wavelength of 560 nm or more and light having a wavelength of 480 nm or less in the case of green, light having a wavelength of 490 nm or more in the case of blue, and light having a wavelength of 580 nm or less in the case of red. It is preferable to adjust the chromaticity coordinates of the NTSC standard or the current CRT using such a color filter. Such chromaticity coordinates can be measured using a general chromaticity coordinate measuring instrument such as BM-7, SR-1 manufactured by Topcon Corporation. The thickness of the color filter layer may be about 0.5 to 20 μm.

  Further, an optical thin film such as a dielectric multilayer film may be used instead of the color filter.

  The fluorescence conversion layer absorbs light from the light emitting element and emits light from the phosphor in the fluorescence conversion layer, thereby performing color conversion of the emission color. The composition is formed from three of a binder, a fluorescent material, and a light absorbing material.

  Basically, a fluorescent material having a high fluorescence quantum yield may be used, and it is preferable that the fluorescent material has strong absorption in the emission wavelength region. Specifically, a fluorescent material having an emission maximum wavelength λmax of the fluorescence spectrum of 580 to 630 nm is preferable. In practice, laser dyes are suitable, such as rhodamine compounds, perylene compounds, cyanine compounds, phthalocyanine compounds (including subphthalocyanines), naphthalimide compounds, condensed ring hydrocarbon compounds, condensed heterocyclic rings. A compound, a styryl compound, or the like may be used.

  Basically, a material that does not quench fluorescence can be selected as the binder, and a binder that can be finely patterned by photolithography, printing, or the like is preferable. Further, a material that is not damaged during the film formation of the positive electrode ITO or IZO is preferable.

  The light absorbing material is used when the light absorption of the fluorescent material is insufficient, but may not be used when not necessary. As the light absorbing material, a material that does not quench the fluorescence of the fluorescent material may be selected.

  By using such a fluorescence conversion filter layer, preferable x and y values can be obtained in the CIE chromaticity coordinates. The thickness of the fluorescence conversion filter layer may be about 0.5 to 20 μm.

  The overcoat layer is not particularly required in the present invention, and the function of the overcoat layer can be shared by directly forming a silica film on the color filter layer and the fluorescence conversion layer. When an overcoat layer is provided if necessary, a thermosetting resin or an ultraviolet curable resin is preferable, and the thermosetting resin is particularly preferable because the surface of the organic layer is further flattened by heat during curing. Among these, polysilsesquioxane resin (ladder silicon resin) and acrylic resin are particularly preferable. One kind of resin may be used, or two or more kinds of resins may be used in combination. The overcoat layer is usually applied on a substrate, a fluorescence conversion layer and / or a color filter layer, and is formed by thermal curing or ultraviolet curing. The curing temperature of a normal thermosetting resin is about 140 to 180 ° C. In the case of an ultraviolet curable resin, the UV light is usually irradiated so that the integrated light quantity is 1000 to 10,000 mJ.

  Also, when diverting a color filter for liquid crystal display, the roughness of the surface is measured by AFM and Rmax is 30 nm or less, and even if it is a single shot, there is even a slight irregularity defect that greatly exceeds 30 nm. Must not. Providing the above-described surface flattening overcoat layer having a thickness of 1 μm or more so as not to cause such large protrusions is also effective in taking measures against image quality degradation such as “black spot” and “short”.

  Next, an organic light emitting structure preferable as the light emitting device of the present invention will be described. As shown in FIG. 1, the organic light emitting structure is usually laminated on a silica film. An example of the configuration is a structure in which a positive electrode, a hole injecting and transporting layer, a light emitting layer, an electron injecting and transporting layer, and a negative electrode, which are transparent electrodes, are sequentially stacked.

  The organic light-emitting structure of the present invention is not limited to the above example, and can have various configurations. For example, the electron injection / transport layer is omitted or integrated with the light-emitting layer, or the hole injection / transport layer and the light-emitting layer And may be mixed. Further, there may be two or more light emitting layers.

  The negative electrode and the positive electrode can be formed by vapor deposition or sputtering, and the organic layer such as the light-emitting layer can be formed by vacuum vapor deposition or the like. Each of these films can be patterned by a method such as mask vapor deposition or etching after film formation, if necessary, whereby a desired light emission pattern can be obtained.

  Next, the organic material layer provided in the organic light emitting device of the present invention will be described.

  This organic layer includes a light emitting layer. A light emitting layer consists of a laminated film of at least one kind of organic compound thin film involved in the light emitting function.

  The light emitting layer has a hole (hole) and electron injection function, a transport function thereof, and a function of generating excitons by recombination of holes and electrons. By using a relatively electronically neutral compound for the light emitting layer, electrons and holes can be injected and transported easily and in a balanced manner.

  If necessary, the light emitting layer may further include a hole injecting and transporting layer, an electron injecting and transporting layer, etc. in addition to the narrowly defined light emitting layer.

  The hole injecting and transporting layer has a function of facilitating the injection of holes from the hole injecting electrode, a function of stably transporting holes, and a function of blocking electrons. The electron injecting and transporting layer is composed of electrons from the electron injecting electrode. It has a function of facilitating the injection of electrons, a function of stably transporting electrons, and a function of blocking holes. These layers increase and confine holes and electrons injected into the light emitting layer, optimize the recombination region, and improve the light emission efficiency.

  The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited and vary depending on the forming method, but are usually about 5 to 500 nm, particularly 10 to 300 nm. It is preferable.

  The thickness of the hole injecting and transporting layer and the thickness of the electron injecting and transporting layer may be the same as the thickness of the light emitting layer or about 1/10 to 10 times depending on the design of the recombination / light emitting region. When the hole / electron injection layer and the transport layer are separated, the injection layer is preferably 1 nm or more, and the transport layer is preferably 1 nm or more. The upper limit of the thickness of the injection layer and the transport layer at this time is usually about 500 nm for the injection layer and about 500 nm for the transport layer. Such a film thickness is the same when two injection transport layers are provided.

  The light emitting layer of the organic light emitting element contains a fluorescent material which is a compound having a light emitting function. Examples of such a fluorescent substance include at least one selected from compounds such as those disclosed in JP-A 63-264692, such as quinacridone, rubrene, and styryl dyes. In addition, quinoline derivatives such as metal complex dyes having 8-quinolinol or a derivative thereof such as tris (8-quinolinolato) aluminum as a ligand, tetraphenylbutadiene, anthracene, perylene, coronene, 12-phthaloperinone derivatives, and the like can be given. Further, phenylanthracene derivatives described in JP-A-8-12600, tetraarylethene derivatives described in JP-A-8-12969, and the like can be used.

  Moreover, it is also preferable to use it in combination with a host substance that can emit light by itself, and it is also preferable to use it as a dopant. In such a case, the content of the compound in the light emitting layer is preferably 0.01 to 10% by volume, more preferably 0.1 to 5% by volume. Particularly in the case of rubrene, 0.01 to 20% by volume is preferable. When used in combination with a host material, the emission wavelength characteristic of the host material can be changed, light emission shifted to a longer wavelength can be achieved, and the light emission efficiency and stability of the device can be improved.

  As the host substance, a quinolinolato complex is preferable, and an aluminum complex having 8-quinolinol or a derivative thereof as a ligand is more preferable. Examples of such aluminum complexes are those disclosed in JP-A 63-264692, JP-A 3-255190, JP-A 5-70773, JP-A-5-258859, JP-A 6-215874, and the like. Can be mentioned.

  Specifically, first, tris (8-quinolinolato) aluminum, bis (8-quinolinolato) magnesium, bis (benzo {f} -8-quinolinolato) zinc, bis (2-methyl-8-quinolinolato) aluminum oxide, tris (8-quinolinolato) indium, tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatolithium, tris (5-chloro-8-quinolinolato) gallium, bis (5-chloro-8-quinolinolato) calcium, 5,7-dichloro-8-quinolinolato aluminum, tris (5,7-dibromo-8-hydroxyquinolinolato) aluminum, poly [zinc (II) -bis (8-hydroxy-5-quinolinyl) methane], etc. There is.

  Further, in addition to 8-quinolinol or a derivative thereof, an aluminum complex having another ligand may be used, and examples thereof include bis (2-methyl-8-quinolinolato) (phenolato) aluminum (III). Bis (2-methyl-8-quinolinolato) (ortho-cresolato) aluminum (III), bis (2-methyl-8-quinolinolato) (meta-cresolato) aluminum (III), bis (2-methyl-8-quinolinolato) ) (Para-cresolato) aluminum (III), bis (2-methyl-8-quinolinolato) (ortho-phenylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (meta-phenylphenolato) Aluminum (III), bis (2-methyl-8-quinolinolato) (para-phenylphenolato) aluminum III), bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolato) aluminum (III) Bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum (III), bis (2-Methyl-8-quinolinolato) (3,5-di-tert-butylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum (III) Bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,3,6-trimethylphenolato) aluminum (III), bis (2-methyl-8-quinolinolato) (2,3,5,6-tetramethylphenolato) aluminum (III), bis (2-methyl) -8-quinolinolato) (1-naphtholato) aluminum (III), bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) (ortho- Phenylphenolato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) (para-phenylphenolato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) (meta-phenylphenol) Lato) aluminum (III), bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolato) aluminum (III), Bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolato) aluminum (III), bis (2-methyl-4-ethyl-8-quinolinolato) (para-cresolato) aluminum (III), bis (2-methyl-4-methoxy-8-quinolinolato) (para-phenylphenolato) aluminum (III), bis (2-methyl-5-cyano-8-quinolinolato) (ortho-cresolato) aluminum (III), bis (2-methyl-6-trifluoromethyl-8-quinolinolato) (2-naphtholato) aluminum (III), and the like.

  As other host materials, phenylanthracene derivatives described in JP-A-8-12600, tetraarylethene derivatives described in JP-A-8-12969, and the like are also preferable.

  The light emitting layer may also serve as an electron transport layer. In such a case, it is preferable to use tris (8-quinolinolato) aluminum or the like. What is necessary is just to vapor-deposit these fluorescent substances.

  The light emitting layer is preferably a mixed layer of at least one hole injecting / transporting compound and at least one electron injecting / transporting compound, if necessary, and further contains a dopant in the mixed layer. It is preferable to make it. The content of the compound in such a mixed layer is preferably 0.01 to 20% by volume, more preferably 0.1 to 15% by volume.

  In the mixed layer, a carrier hopping conduction path can be formed, so that each carrier moves in a polar advantageous substance, and carrier injection of the opposite polarity is less likely to occur. There is an advantage of extending. Moreover, by including the above-mentioned dopant in such a mixed layer, the emission wavelength characteristic of the mixed layer itself can be changed, the emission wavelength can be shifted to a long wavelength, and the emission intensity is increased. The stability of the element can also be improved.

  The hole injecting / transporting compound and the electron injecting / transporting compound used in the mixed layer may be selected from the hole injecting / transporting compound and the electron injecting / transporting compound described below, respectively.

As the electron injecting and transporting compound, it is preferable to use a quinoline derivative, a metal complex having 8-quinolinol or a derivative thereof as a ligand, particularly tris (8-quinolinolato) aluminum (Alq ₃ ). Moreover, it is also preferable to use the above phenylanthracene derivatives and tetraarylethene derivatives.

  As the compound for the hole injecting and transporting layer, it is preferable to use amine derivatives having strong fluorescence, such as triphenyldiamine derivatives, styrylamine derivatives, and amine derivatives having an aromatic condensed ring.

  The mixing ratio in this case depends on the carrier mobility and carrier concentration of each, but generally the mass ratio of hole injecting / transporting compound / electron injecting / transporting compound is 1/99 to 99/1, more preferably It is preferable to be about 10/90 to 90/10, particularly preferably about 20/80 to 80/20.

  In addition, the thickness of the mixed layer is preferably equal to or greater than the thickness corresponding to one molecular layer and less than the thickness of the organic compound layer. Specifically, the thickness is preferably 1 to 100 nm, more preferably 5 to 60 nm, and particularly preferably 5 to 50 nm.

  In addition, as a method for forming the mixed layer, co-evaporation is preferably performed by evaporating from different evaporation sources, but when the vapor pressure (evaporation temperature) is the same or very close, the mixture is previously mixed in the same evaporation board, It can also be deposited. In the mixed layer, it is preferable that the compounds are uniformly mixed, but in some cases, the compounds may be present in an island shape. In general, the light emitting layer is formed to have a predetermined thickness by depositing an organic fluorescent material or coating the light emitting layer by dispersing it in a resin binder.

  Examples of the hole injecting and transporting compound include JP-A 63-295695, JP-A 2-191694, JP-A 3-792, JP-A-5-234681, and JP-A-5-239455. Various organic compounds described in JP-A-5-299174, JP-A-7-126225, JP-A-7-126226, JP-A-8-100192, EP0650955A1, and the like can be used. For example, tetraarylbenzidine compounds (triaryldiamine or triphenyldiamine: TPD), aromatic tertiary amines, hydrazone derivatives, carbazole derivatives, triazole derivatives, imidazole derivatives, oxadiazole derivatives having amino groups, polythiophenes, etc. . These compounds may be used alone or in combination of two or more. When two or more types are used in combination, they may be laminated as separate layers or mixed.

Electron injecting and transporting compounds include quinoline derivatives, oxadiazole derivatives, perylene derivatives, pyridine derivatives, such as organometallic complexes having 8-quinolinol or a derivative thereof such as tris (8-quinolinolato) aluminum (Alq ₃ ) as a ligand. Pyrimidine derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorene derivatives, and the like can be used.

  For the formation of the light emitting layer, the hole injecting and transporting layer, and the electron injecting and transporting layer, it is preferable to use a vacuum deposition method because a homogeneous thin film can be formed. When the vacuum deposition method is used, a homogeneous thin film having an amorphous state or a crystal grain size of 0.2 μm or less can be obtained. If the crystal grain size exceeds 0.2 μm, non-uniform light emission occurs, the drive voltage of the element must be increased, and the charge injection efficiency is also significantly reduced.

Although the conditions of vacuum deposition are not specifically limited, It is preferable to set it as the vacuum degree of 10 < ^-4 > Pa or less, and a vapor deposition rate to be about 0.01-1 nm / sec. Moreover, it is preferable to form each layer continuously in a vacuum. If formed continuously in a vacuum, impurities can be prevented from adsorbing to the interface of each layer, so that high characteristics can be obtained. Further, the driving voltage of the element can be lowered, and the generation / growth of dark spots can be suppressed.

  In the case of using a vacuum deposition method for forming each of these layers, when a plurality of compounds are contained in one layer, it is preferable to co-deposit each boat containing the compounds by individually controlling the temperature.

  In the present invention, each organic layer may be formed by a coating method. By forming the organic layer by a coating method, the element can be formed more easily, and the production efficiency can be improved and the price of the element can be reduced. In particular, using a microgravure method, etc., each light emitting layer having a thin film thickness of about 30 to 100 nm is separately coated in a stripe shape of about 100 μm width at a pitch of 100 μm, and the above-mentioned flexible barrier film is used as a substrate Thus, a method using precise coating accuracy control for printing roll-to-roll is preferable.

  Examples of known polymer light-emitting materials for organic light-emitting used in the light-emitting layer include polymer compounds such as polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like. Poly (2-decyloxy-1,4-phenylene) (DO-PPP), poly [2,5-bis [2- (N, N, N-triethylammonium) ethoxy] -1,4-phenylene-alt-1 , 4-phenylene] dibromide (PPP-NEt3 +), poly [2- (2′-ethylhexyloxy) -5-methoxy-1,4-phenylenevinylene] (MEH-PPV), poly (5-methoxy- (2 -Propanoxysulfonide) -1,4-phenylenevinylene) (MPS-PPV), poly [2,5-bis (hexyl) Oxy-1,4-phenylene)-(1-cyanovinylene)] (CN-PPV), poly [2- (2'-ethylhexyloxy) -5-methoxy-1,4-phenylene- (1-cyanovinylene)] ( MEH-CN-PPV) and poly (dioctylfluorene) (PDF).

  Alternatively, as a precursor of a known polymer light emitting material for organic light emission, for example, a poly (p-phenylene) precursor (Pre-PPP), a poly (p-phenylene vinylene) precursor (Pre-PPV), a poly ( A p-naphthalene vinylene) precursor (Pre-PNV) or the like can be used.

  A known low-molecular light-emitting material for organic light emission and a known polymer material such as polycarbonate (PC), polymethyl methacrylate (PMMA), polycarbazole (PVCz) and the like may be mixed and used.

  Moreover, you may use the additive for viscosity adjustment as needed. In particular, when the light emitting layer and the hole injection layer are formed by uniform thin film printing with a thickness of 100 nm or less, it is necessary to dilute the light emitting polymer to an extremely low concentration to prevent transfer pattern flow and transfer from the plate to the substrate. In order to improve the properties, a minute amount of a thickener or gelling agent that increases the viscosity or the elastic modulus of the solution without affecting the light emission characteristics of organic light emission may be used as an additive.

  As well-known polymer charge transport materials, hole transport materials include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, aryl Amine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, polysilanes (N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, polythiophene derivatives, polyphenols Ren derivatives, polyphenylene vinylene derivatives, polymer compounds such as polyfluorene derivatives, and the like.

  Examples of the electron transporting material include polymer compounds such as polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.

  Solvents used when forming these polymer materials by a coating method include, for example, ethylene glycol, propylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol moethyl ether, triethylene glycol monomethyl ether, triethylene glycol. Examples include moethyl ether, glycerin, N, N-dimethylformamide, N-methyl-2-pyrrolidone, cyclohexanone, 1-propanol, octane, nonane, decane, xylene, diethylbenzene, trimethylbenzene, nitrobenzene and the like.

  The organic material is preferably dissolved in the coating solvent so that each concentration is 0.1 to 5% (mass percentage). With respect to the coating, any coating method using any solution such as a spin coating method, a spray coating method, a dip coating method, and a flexographic method can be used. After application, the element may be heated with a hot plate or the like for the drying operation of the solvent. The heating is preferably performed at a temperature equal to or lower than the Tg (glass transition temperature) of the organic light emitting material, and is usually about 50 to 80 ° C., and preferably dried under reduced pressure or under an inert atmosphere.

  The thickness per organic layer is preferably 0.5 to 1000 nm, more preferably 10 to 500 nm, when applied by a coating method. Moreover, when it is based on vapor deposition methods, such as a vacuum vapor deposition method, it is about 1-500 nm.

The positive electrode (hole injection electrode) material is preferably one that can efficiently inject holes into a hole injection layer or the like, and a substance having a work function of 4.5 eV to 5.5 eV is preferable. Specifically, the main composition is any one of tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), and zinc oxide (ZnO). Those are preferred. These oxides may deviate somewhat from their stoichiometric composition. The mixing ratio of SnO ₂ to In ₂ O ₃ is preferably 1 to 20% by mass, more preferably 5 to 12% by mass. The mixing ratio of ZnO to In ₂ O ₃ in IZO is usually about 12 to 32% by mass.

The hole injection electrode may contain silicon oxide (SiO ₂ ) in order to adjust the work function. The content of silicon oxide (SiO ₂ ) is preferably about 0.5 to 10% in terms of the molar ratio of SiO _{2 to} ITO. The inclusion of SiO _2, the work function of ITO is increased.

  The electrode on the light extraction side preferably has an emission wavelength band, usually 400 to 700 nm, and particularly has a light transmittance of 50% or more, more preferably 80% or more, particularly 90% or more for each emitted light. If the transmittance is too low, light emission from the light emitting layer itself is attenuated, and it becomes difficult to obtain luminance necessary for the light emitting element.

  The thickness of the electrode is preferably 50 to 500 nm, particularly 50 to 300 nm. Further, the upper limit is not particularly limited, but if it is too thick, there is a concern about a decrease in transmittance or peeling. If the thickness is too thin, a sufficient effect cannot be obtained, and there is a problem in terms of film strength at the time of manufacture.

  As the negative electrode, the following can be used as necessary as an electrode having an electron injecting property. For example, metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Sn, Zn, Zr, etc., or a two-component or three-component alloy system containing them to improve stability For example, Ag · Mg (Ag: 0.1 to 50 at%), Al·Li (Li: 0.01 to 14 at%), In · Mg (Mg: 50 to 80 at%), Al · Ca (Ca: 0. 01 to 20 at%).

  In addition, these alkali metal monovalent ions (for example, Li, Na, K), alkaline earth metal divalent ions (for example, Pt, Zn), and trivalent ions (for example, Al, In) are oxygen complexes (for example, acetylacetone). , Acetic acid, oxalic acid, etc.) may be formed, and these may be dissolved in a solution and applied to form a thin layer cathode.

  The thickness of the negative electrode thin film may be a certain thickness that allows sufficient electron injection, and may be 0.1 nm or more, preferably 0.5 nm or more, particularly 1 nm or more. Moreover, although there is no restriction | limiting in particular in the upper limit, A normal film thickness should just be about 1-500 nm.

Furthermore, in order to prevent deterioration of the organic layer and electrode of the element, it is preferable to seal the element with a sealing plate or the like. The sealing plate adheres and seals the sealing plate using an adhesive resin layer in order to prevent moisture from entering. Sealing gas, Ar, He, an inert gas such as _{N 2} is preferable. The moisture content of the sealing gas is preferably 100 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. There is no particular lower limit to the water content, but it is usually about 0.1 ppm.

  The material for the sealing plate is preferably the same as the material for the substrate mentioned above. The sealing plate may be held at a desired height by adjusting the height using a spacer. Examples of the material for the spacer include resin beads, silica beads, glass beads, glass fibers, and the like, and glass beads are particularly preferable.

  In addition, when the recessed part is formed in the sealing plate, the preferable size of the spacer may be in the above range, but the range of 2 to 8 μm is particularly preferable.

Furthermore, a desiccant, preferably CaH ₂ , may be enclosed inside.

  The adhesive is not particularly limited as long as stable adhesive strength can be maintained and airtightness is good, but it is preferable to use a cationic curing type ultraviolet curing epoxy resin adhesive.

  Next, an example is shown with a comparative example and the present invention is explained more concretely.

Example 1
Production of Organic Light-Emitting Element 3 As shown in FIG. 1, polyterephthalate having a thickness of 200 μm and having a transparency with a total light transmittance of 90% or more and Tg: heat resistance of 79 ° C. is used as the base material 2. It was. Next, a uniform mixed solution consisting of 25% by mass of bifunctional epoxy acrylate (Showa Polymer: VR-60-LAV), 50% by mass of diethylene glycol, 24% by mass of ethyl acetate, and 1% by mass of silane coupling agent was obtained with a spin coater. It was applied, dried by heating at 80 ° C. for 10 minutes, and further cured by UV irradiation to form a 2 μm resin layer. Next, the film on which the organic layer is formed is set in a vacuum chamber of a sputtering apparatus, and vacuum is drawn up to 10 ⁻⁴ Pa level, and argon is introduced into a mixed gas of oxygen and nitrogen as a discharge gas by 0.5 Pa at a partial pressure. . When the atmospheric pressure was stabilized, discharge was started, plasma was generated on the Si ₃ N ₄ target, and a sputtering process was started. When the process was stabilized, the shutter was opened and formation of the lower layer of the silicon oxynitride layer on the film was started. When the 5 nm film was deposited, the shutter was closed to complete the film formation. The element concentration ratio O / (O + N) of the upper layer of the silicon oxynitride layer formed under these conditions was 0.2 as a result of measurement by X-ray photoelectron spectroscopy (ESCA). Subsequently, 0.5 Pa was introduced at a partial pressure of argon as a discharge gas, and a mixed gas of oxygen and nitrogen was introduced as a discharge gas. When the atmospheric pressure was stabilized, discharge was started, plasma was generated on the Si ₃ N ₄ target, and a sputtering process was started. When the process was stabilized, the shutter was opened and formation of the upper layer of the silicon oxynitride layer on the film was started. When the 95 nm film was deposited, the shutter was closed to complete the film formation. The element concentration ratio O / (O + N) of the upper layer of the silicon oxynitride layer formed under these conditions was measured by ESCA to be 0.3. The atmosphere was introduced into the vacuum chamber, and the silicon oxynitride layer-forming film on which the silicon oxynitride layer was formed was taken out.

Further, ashing was performed for 10 minutes with oxygen plasma (2 kW output, substrate temperature 200 ° C.). By this treatment, the surface of the silicon oxynitride layer is further cleaned and becomes a flatter and complete a-SiO ₂ passivation layer.

Next, an ITO transparent electrode (hole injection electrode) was formed and patterned so as to constitute a pixel of 64 dots × 7 lines (100 × 100 μm per pixel) with a film thickness of 85 nm. And the board | substrate with which the patterned hole injection electrode was formed was ultrasonically cleaned using neutral detergent, acetone, and ethanol, and it pulled up from boiling ethanol and dried. Thereafter, UV / O ₃ cleaning was performed.

Next, the substrate was moved to the film formation chamber, fixed to the substrate holder of the vacuum deposition apparatus, and the inside of the tank was depressurized to 1 × 10 ⁻⁴ Pa or less. Then, poly (thiophene-2,5-diyl) as a hole injection layer is formed to a thickness of 10 nm, and TPD doped with 1% by mass of rubrene as a hole transport layer and a yellow light-emitting layer is co-evaporated to 5 nm. The film was formed to a film thickness. The concentration may be determined based on the color balance of the emission color, and depends on the light intensity and wavelength spectrum of the blue light emitting layer to be formed thereafter. Further, 4′-bis [(1,2,2-triphenyl) ethenyl] biphenyl was grown to 50 nm as the blue light emitting layer, and Alq ₃ was grown to 10 nm as the electron transport layer.

Next, AlLi (Li: 7 at%) was evaporated to a thickness of 1 nm, and an Al electrode layer was formed to a thickness of 200 nm to form an organic light emitting element 4. Before sealing as an organic light-emitting device, a desiccant (CaH ₂ ) mixed and fixed in silicon rubber was sealed, and finally sealed with a sealing film 8 in which EVA was coated on a 100 μm-thick PCTFE film. The organic light emitting device 3 was obtained.

The compounds used were as follows: Silane coupling agent: (CH ₃ O) Si (CH ₂ ) ₃ NH ₂
TPD: N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine rubrene: 5,6,11,12-tetraphenylnaphtha Sen PCTFE: Polychlorotrifluoroethylene EVA: Ethylene-vinyl acetate copolymer Preparation of organic light-emitting devices 1, 2 and 4-9 When forming a silicon oxynitride layer lower layer and an upper layer in the same manner as organic light-emitting device 3, discharge gas By changing the partial pressure of oxygen and nitrogen, a silicon oxynitride layer forming film having the element concentration ratio O / (O + N) shown in Table 1 was obtained. With respect to each silicon oxynitride layer forming film, organic light emitting devices 4 to 8 were obtained through the same steps as the organic light emitting device 3 after the next step.

  In addition, the organic light emitting elements 2 and 9 formed only the silicon oxynitride layer lower layer, and the discharge gas of the organic light emitting element 2 was a gas only of oxygen and argon. Moreover, the base material of the organic light emitting element 1 is not formed with a silicon oxynitride layer.

A direct-current voltage is applied to each of the organic light-emitting devices produced as described above, and the device is continuously driven at a constant current density of 50 mA / cm ² to evaluate the luminance half time and dark spots. Table 1 shows the results.

  From Table 1, it can be seen that the configuration of the present invention significantly increases the luminance half-life time and significantly suppresses dark spots.

Example 2
Preparation of Organic Light-Emitting Element 12 As the substrate 2, polyterephthalate having a thickness of 100 μm and having transparency with a total light transmittance of 90% or more and Tg: 79 ° C. was used. Next, 25% by mass of bifunctional epoxy acrylate (Showa Polymer: VR-60-LAV), 50% by mass of diethylene glycol, 24% by mass of ethyl acetate, and 1% by mass of the silane coupling agent used in Example 1 were obtained. The mixed solution was applied with a spin coater, heated and dried at 80 ° C. for 10 minutes, and further cured by UV irradiation to form a 100 μm resin layer. Next, a 20% by mass solution of polysilazane partially methyl-modified product (substitute product of 10 at% hydrogen in the structure) of dibutyl ether (DBE) (L710, manufactured by Tonen Co., Ltd., Pd catalyst-containing product) is added to nitrogen (80 %) And oxygen (20%) in a mixed gas, coated by a dip coating method, heated and dried, and then treated with an excimer lamp 60 mw / cm ^{2 to} obtain a dense thickness on the substrate. A silicon oxynitride layer containing a minute methyl group having a thickness of about 150 nm was obtained. The element concentration ratio O / (O + N) of the formed silicon oxynitride layer lower layer was measured by ESCA and found to be 0.2. Furthermore, nitrogen (80%) was added to a coating solution of a xylene solution of perhydropolysilazane (Mn = 1000) similar to the above (concentration 20 mass%: L710 manufactured by Tonen Co., Ltd., Pd catalyst containing product of several hundred nm). %) And oxygen (20%) in a mixed gas, coated by a dip coating method, heated and dried, and then treated with an excimer lamp 60 mw / cm ^{2 to} obtain a dense thickness of about 100 nm. A silicon oxynitride layer forming film having a small silicon oxynitride film layer was obtained. The element concentration ratio O / (O + N) of the upper layer of the silicon oxynitride layer was measured by ESCA to be 0.3.

  After the next step, the organic light emitting device 12 was obtained through the same steps as the organic light emitting device 3.

Organic light emitting device 11, 13-18
When the silicon oxynitride layer lower layer and the upper layer are formed in the same manner as in the organic light emitting device 12, by changing the mixing ratio of oxygen and nitrogen of the bubbling gas, the acid having the element concentration ratio O / (O + N) shown in Table 2 A silicon nitride layer forming film was obtained. With respect to each silicon oxynitride layer forming film, organic light emitting devices 13 to 18 were obtained through the same steps as the organic light emitting device 3 after the next step.

  In addition, the organic light emitting elements 11 and 18 formed only the silicon oxynitride layer lower layer, and the bubbling gas of the organic light emitting element 11 was a gas containing only oxygen.

  In the same manner as in Example 1, the luminance half-life and dark spots were evaluated for each of the organic light-emitting devices produced above, and the results are shown in Table 2.

  From Table 2, it can be seen that in the organic light-emitting device of the present invention, the luminance half-time is significantly increased and dark spots are also significantly suppressed.

DESCRIPTION OF SYMBOLS 1 Light emitting element 2 Base material 3 Silicon oxynitride film 4 Light emitting element structure 5 Lower electrode 6 Light emitting layer 7 Upper electrode 8 Sealing film

Claims (4)

  A light-emitting element having a light-transmitting lower electrode formed on a resin substrate, a light-emitting layer, and an upper electrode, and comprising at least a silicon oxynitride film between the light-emitting layer and the resin substrate A light-emitting element having a layer.   The silicon oxynitride film is a layer made of a silicon oxynitride film obtained by applying at least polysilazane between the light emitting layer and the resin base material and performing an oxidation treatment. Light emitting element.   When the silicon oxynitride film has two or more layers, the element concentration ratio O / (O + N) of the silicon oxynitride film closest to the resin base material is the element concentration ratio O / (O + N) of the upper silicon oxynitride film. The light-emitting element according to claim 1, wherein the light-emitting element is smaller.   The light emitting element according to any one of claims 1 to 3, wherein the silicon oxynitride film is subjected to an oxidation treatment with ultraviolet light of 120 to 300 nm.

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