JP2009094050A - Light-emitting element or display element, and manufacturing method of them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a light-emitting element or a display element which is thin and is hardly cracked. <P>SOLUTION: The light-emitting element or the display element has a resin film or a resin layer, a glass substrate, a light-emitting device laminated body or a display device laminated body, and a gas barrier film in that order. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a light-emitting element or a display element and a method for manufacturing the same.

  Conventionally, it has been studied to use a glass substrate or a gas barrier film for an organic EL element. For example, Patent Literature 1 describes that a transparent gas barrier film provided with an ultrathin plate glass and a transparent resin layer is used as a sealing material for an organic EL element. Patent Document 2 describes an organic electroluminescent element having a glass substrate and a panel protective film. In such an organic electroluminescent device, the cap prevents moisture from entering the device.

JP 2004-79432 A JP 2005-63976 A

However, when a glass substrate is used, there is a problem that it is easily broken. In addition, if it is difficult to break, it is necessary to increase the thickness of the glass substrate, resulting in a problem that the thickness of the element increases. Further, as in Patent Document 2 (Japanese Patent Laid-Open No. 2005-63976), when a cap is used, a space is opened between the light emitting device stack or the display device stack. This space also increases the thickness of the element. Furthermore, as an attempt to fabricate an element without using a glass substrate, it is also considered to substitute a gas barrier film without using a glass substrate, but there is a problem that dimensional accuracy deteriorates in the element fabrication stage. is there.
An object of the present invention is to provide a light-emitting element or a display element that uses a glass substrate and is thin and hardly broken.

As a result of intensive studies by the present inventors under the above problems, it has been found that the above problems can be solved by the following means.
(1) A light-emitting element or display element having a resin film or resin layer, a glass substrate, a light-emitting device laminate or a display device laminate, and a gas barrier film in that order.
(2) The light-emitting element or display element according to (1), wherein the resin film or resin layer has a circularly polarizing function.
(3) The light emitting element or display element as described in (1) whose resin film or resin layer has a light-diffusion function.
(4) The light emitting element or display element of any one of (1)-(3) whose thickness of a glass substrate is 100 micrometers-300 micrometers.
(5) The light emitting element or display element of any one of (1)-(4) which has an contact bonding layer between a light emitting device laminated body or a display device laminated body, and a gas barrier film.
(6) The light-emitting element or display element according to any one of (1) to (5), wherein the gas barrier film has an adhesive layer.
(7) The light emitting element or display element of any one of (1)-(6) which has an contact bonding layer between a resin film and a glass substrate.
(8) The light emitting element or display element of any one of (1)-(7) whose thickness of a resin film or a resin layer is 10-1000 micrometers.
(9) The light emitting element or display element of any one of (1)-(8) which has a smooth layer between a glass substrate and a light emitting device laminated body or a display device laminated body.
(10) The light-emitting element or display element according to any one of (1) to (9), wherein the smooth layer has a thickness of 0.5 to 10 μm.
(11) The light emitting device or the display device according to any one of (1) to (10), wherein the thickness unevenness of the glass substrate is 100 μm or less.
(12) The gas barrier film according to any one of (1) to (11), wherein the gas barrier film has at least one organic region and at least one inorganic region on the base film.
(13) The method for manufacturing a light emitting device or a display device according to any one of (1) to (12), wherein after the resin film and the glass substrate are bonded together, the light emitting device laminate is etched. Or a manufacturing method characterized by providing a display device laminated body.
(14) A light emitting device or a display device manufactured by the manufacturing method of (13).
(15) The light-emitting element or the display element according to any one of (1) to (12) and (14), wherein the light-emitting element or the display element is an organic EL element.

According to the present invention, it is possible to provide a light-emitting element or a display element that is thin and hardly cracked.
In particular, in the present invention, since the etching can be performed after the film is bonded to the glass substrate, the etching operation is facilitated. That is, if an attempt is made to etch a single glass substrate, the glass substrate is easily broken, and thus etching must be performed precisely and carefully. However, the present invention does not have such a problem. Also, when etching after assembling the element to some extent, what is etched in the state of an empty cell like a liquid crystal display device is easy to etch, but only after providing a light emitting device stack like an organic EL element, In the case of an element that cannot be etched, the light-emitting device laminate deteriorates, and it is also problematic to perform etching after assembling the element to some extent. The present invention is extremely useful in that all of these problems can be avoided.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.

The light-emitting element or display element of the present invention is characterized by having a resin film or resin layer, a glass substrate, a light-emitting device laminate or a display device laminate, and a gas barrier film in that order. The light-emitting element or display element of the present invention will be described below with reference to the drawings. Needless to say, the light-emitting element or the display element of the present invention is not limited thereto.
FIG. 1 is a schematic view of a light emitting element or a display element of the present invention, wherein 1 is a resin film or resin layer, 2 is a glass substrate, and 3 is a light emitting device laminate or a display device laminate. Reference numerals 4 denote gas barrier films, respectively.
In the present invention, by using the resin film or resin layer 1 and the glass substrate 2 in combination, even if the glass substrate is thinned, it is difficult to break in an operation such as etching, which is extremely useful. Further, by using the gas barrier film 4 as the sealing material, the thickness of the element can be made thinner than sealing with a cap or the like. Here, the light-emitting device laminate or the display device laminate is a portion that forms the core of the light-emitting element or the display element, and usually includes a pair of electrode layers and an organic compound layer provided between the electrode layers. It is a laminate.
The light emitting element or the display element in the present invention may have a constituent layer other than those described above, for example, between the light emitting device laminate or the display device laminate 3 and the gas barrier film 4 and / or the resin film and the glass. The structure which has an contact bonding layer between the board | substrates 2 is mentioned. At this time, it is preferable to use a gas barrier film or a resin film with an adhesive layer because the manufacturing process is simplified. It is also preferable to provide a smooth layer between the glass substrate 2 and the light emitting device laminate or the display device laminate 3. Furthermore, it is also preferable to provide a passivation layer between the light emitting device laminate or the display device laminate 3 and the gas barrier film 4.

(Resin film or resin layer)
The resin film or resin layer in the present invention is mainly composed of a resin, and a film-like one may be attached, or a layer-like one may be provided by applying a resin composition or the like. The material of the resin film or the resin layer is not particularly defined. For example, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamide Imide resin, polyether imide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring Examples thereof include thermoplastic resins such as modified carbonate resins, alicyclic modified polycarbonate resins, and acryloyl compounds, and heat or photocurable resins such as acrylic resins and epoxy resins. Further, the resin film or the resin layer needs to be transparent in the case of a bottom emission type light emitting element or display element, but may not be transparent in the case of a top emission type light emitting element or display element.
Although the thickness of a resin film or a resin layer is not specifically defined, 10-1000 micrometers is preferable and 20-200 micrometers is more preferable.
The resin film or resin layer in the present invention may have a circular polarization function or a light diffusion function. With such a structure, the thickness of the element can be further reduced in the case of a bottom emission type light emitting element or display element. Here, in order to provide the circular polarization function or the light diffusion function, for example, the method described in JP-A-8-321381, JP-A-9-127858, JP-A-7-142170, or the like is employed. Can do.

(Glass substrate)
As the glass substrate in the present invention, a glass substrate used for a display element or a light emitting element can be widely adopted. In the present invention, by using together with a resin film or a resin layer, the glass substrate can be made difficult to break even if the thickness of the glass substrate is reduced. In particular, etching after laminating a resin film or resin layer and a glass substrate is easy to produce because it is difficult to break during etching, and furthermore, only one side can be etched, so the thickness of the glass substrate Unevenness can be reduced. For example, in the present invention, the thickness unevenness of the glass substrate can be 100 μm or less, and further can be 50 μm or less. The thickness unevenness is preferably 50% or less of the average thickness.
The thickness of the glass substrate can be, for example, 100 μm to 300 μm, and further can be 100 to 200 μm.

(Gas barrier film)
The gas barrier film in the present invention is a film having a barrier layer having a function of blocking oxygen and moisture in the atmosphere. The barrier layer in the present invention may be any layer as long as it is known to have gas barrier ability, but is preferably an organic-inorganic laminated type in which organic regions and inorganic regions or organic layers and inorganic layers are alternately laminated. . Hereinafter, a film having an organic-inorganic laminated barrier layer in which organic regions and inorganic regions or organic layers and inorganic layers are alternately laminated may be referred to as an “organic-inorganic laminated gas barrier film”.
Organic regions and inorganic regions or organic layers and inorganic layers are usually laminated alternately. In the case of an organic region and an inorganic region, a so-called gradient material layer in which each region continuously changes in the film thickness direction may be used. Examples of the gradient materials include a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. , American Vacuum Society) ”, or a continuous layer in which the organic layer and the inorganic layer do not have an interface as disclosed in US Published Patent Application No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layer”, and the inorganic layer and the inorganic region are described as “inorganic layer”.
Although there is no restriction | limiting in particular regarding the number of layers which comprises a cas barrier film, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. In addition, the barrier layer may be provided only on one side of the base film, or may be provided on both sides.

(Base film)
The gas barrier film in the present invention usually uses a plastic film as the base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specifically, as the plastic film, metal support (aluminum, copper, stainless steel, etc.) polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin , Polyamide resin, polyamideimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin Examples thereof include thermoplastic resins such as filn copolymers, fluorene ring-modified polycarbonate resins, alicyclic ring-modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  The gas barrier film of the present invention is preferably made of a heat-resistant material. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate ( PAr: 210 ° C., polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: Japanese Patent Application Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the gas barrier film of the present invention is used in combination with a polarizing plate, it is preferable that the barrier laminate of the gas barrier film faces the inside of the cell and is arranged on the innermost side (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (¼ wavelength plate + (½ wavelength plate) + linear polarizing plate. ) Or a linear barrier plate is used in combination with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.): U100 (pellet) )), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

The gas barrier film of the present invention is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the gas barrier film of the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used for the gas barrier film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, a coating method, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable, and specifically, Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002-361774. The described forming method can be employed.
The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance, but for example, one or more selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Ta, or the like An oxide containing metal, nitride, carbide, oxynitride, oxycarbide, nitride carbide, oxynitride carbide, or the like can be used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. . These may contain other elements as secondary components.
Although it does not specifically limit regarding the thickness of the said inorganic layer, It is preferable to exist in the range of 5 nm-500 nm, More preferably, it is 10 nm-200 nm. Two or more inorganic layers may be laminated. In this case, each layer may have the same composition or a different composition. Further, as described above, a layer whose interface with the organic layer is not clear as disclosed in US Patent Publication No. 2004-46497 and whose composition changes continuously in the film thickness direction may be used.

(Organic layer)
In the present invention, the organic layer is usually a polymer layer. The organic layer may be provided by applying a polymer solution, or a hybrid coating method containing an inorganic substance as disclosed in JP 2000-323273 A or JP 2004-25732 A may be used. . Alternatively, a polymer layer may be formed by polymerizing a polymer precursor (for example, a monomer) after film formation.

In the present invention, the organic layer is preferably composed of a polymer of a radically polymerizable compound and / or a cationically polymerizable compound having an ether group as a functional group as a polymer.
(Polymerizable compound)
The polymerizable compound used in the present invention is a compound having an ethylenically unsaturated bond at the terminal or side chain and / or a compound having epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds (acrylates and methacrylates are collectively referred to as (meth) acrylates), acrylamide compounds, styrene compounds, and anhydrous maleic compounds. An acid etc. are mentioned.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

Although the specific example of a (meth) acrylate type compound is shown below, this invention is not limited to these.

 In addition to the above compounds, for example, compounds described in US Pat. No. 6,083,628 and US Pat. No. 6,214,422 are also preferably used.

The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably 10 nm or less, and more preferably 2 nm or less, as an average roughness (Ra value) of 10 μm square. The film hardness of the organic layer preferably has a pencil hardness of HB or higher, and more preferably H or higher.
The film thickness of the organic layer is not particularly limited, but if it is too thin, it will be difficult to obtain film thickness uniformity, and if it is too thick, cracks will be generated by external force and the barrier performance will deteriorate. From this viewpoint, the thickness of the organic layer is preferably 10 nm to 2000 nm, more preferably 100 nm to 1000 nm.

 Examples of the method for forming the organic layer include a normal solution coating method or a vacuum film forming method. Examples of the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can apply | coat by the extrusion-coating method which uses-. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable.

The monomer polymerization method is not particularly limited, but heat polymerization, light (ultraviolet ray, visible light) polymerization, electron beam polymerization, plasma polymerization, or a combination thereof is preferably used. When performing heat polymerization, the plastic film used as a base material needs to have appropriate heat resistance. In this case, it is necessary that at least the glass transition temperature (Tg) of the plastic film is higher than the heating temperature.
When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Sartomer). Etc.).
The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

 At this time, the polymerization rate of the monomer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. The polymerization rate here means the ratio of the reacted polymerizable groups among all the polymerizable groups (acryloyl group and methacryloyl group) in the monomer mixture.

(Adhesive layer)
The adhesive layer is a layer mainly composed of an adhesive, and usually 70% by weight or more of the adhesive layer is an adhesive, and preferably 80 to 90% by weight of the adhesive layer is an adhesive. .
As the adhesive, those used as an adhesive for a light emitting element or a display element can be widely used, and an epoxy adhesive is preferable. Here, examples of the epoxy adhesive include a thermosetting type and an ultraviolet curing type. When the barrier film absorbs ultraviolet rays, a thermosetting type is preferable. Among thermosetting types, there are a one-component type and a two-component mixed type, and any of them is preferably used in the present invention. In the present invention, an adhesive that becomes colorless and transparent after curing is preferred. Examples of commercially available products include Epotech series made by Daizonichimomori, XNR-5000 series made by Nagase ChemteX, and 3000 series made by ThreeBond.
Moreover, you may employ | adopt the gas barrier film with an adhesive layer by which the adhesive layer was provided in the surface of the gas barrier film. By employing such a gas barrier film, there is an advantage that the manufacturing process is further simplified.
Although it does not specifically limit regarding the thickness of an contact bonding layer, It is preferable that it is the range of 2-100 micrometers, More preferably, it is 5-20 micrometers.

(Smooth layer)
A smooth layer is a layer provided in order to make the surface smooth, and can laminate | stack the next layer easily. As the smooth layer, a known layer used for a light emitting element and a display element can be adopted. For example, it can be provided in accordance with the method for producing a primer coat layer described in paragraph No. 0011 of JP-A-2003-251731.
Although it does not specifically limit regarding the thickness of a smooth layer, It is preferable that it is the range of 0.5-10 micrometers.

(Display element or light emitting element)
Examples of the display element or the light emitting element in the present invention include a liquid crystal display element, an organic EL element, an inorganic EL element, and a fluorescent display element.

Liquid crystal display element A reflective liquid crystal display device has a configuration comprising, in order from the bottom, a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film. . In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.
The type of the liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence) OCB type (Optically Compensated Bend), CPA type (Continuous Pinwheel Alignment), and IPS type (In-Plane Switching) are preferable.

Touch Panel The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

Organic EL element An organic EL element means an organic electroluminescence element. An organic EL element has a cathode and an anode on a surface opposite to a substrate provided with a resin film or a resin layer, and an organic compound layer including a light emitting layer between both electrodes. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.

 As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.

Anode The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. Thus, it can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode. The transparent anode is described in detail in Yutaka Sawada's “New Development of Transparent Electrode Film” published by CMC (1999). When using a plastic substrate with low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed at a low temperature of 150 ° C. or lower is preferable.

Cathode The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials.

 Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, rare earth metals such as indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, a material mainly composed of aluminum is preferable.
The material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The cathode material is described in detail in JP-A-2-15595 and JP-A-5-121172. Further, a dielectric layer made of a fluoride or oxide of an alkali metal or a Group 2 metal may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.

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

Light-Emitting Layer The organic EL element has at least one organic compound layer including a light-emitting layer, and as the organic compound layer other than the organic light-emitting layer, as described above, a hole transport layer, an electron transport layer, a charge Examples of the layer include a block layer, a hole injection layer, and an electron injection layer.

-Organic light emitting layer-
The organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light. The light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of the fluorescent light-emitting material include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatics. Compound, perinone derivative, oxadiazole derivative, oxazine derivative, aldazine derivative, pyralidine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, thiadiazolopyridine derivative, cyclopentadiene derivative, styrylamine derivative, di Typical examples include ketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives. Various metal complexes are, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
Although it does not specifically limit as said transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

  Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds,” Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha.

  Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. In addition, the electron transport layer / electron injection layer may also function as a hole blocking layer.
Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
In addition, a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side. The hole transport layer / hole injection layer may also serve this function.

TFT display element It can be set as a thin film transistor (TFT) image display element. Examples of the method for producing the TFT array include the method described in JP-T-10-512104. Further, this substrate may have a color filter for color display. The color filter may be produced using any method, but it is preferable to use a photolithography technique.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(Production of gas barrier film)
A gas barrier film (sample Nos. 101 to 103) in which an inorganic layer and an organic layer were provided on a base film was produced according to the following procedure. Details of the structure of each gas barrier film are as shown in Table 1. Polyethylene naphthalate (PEN, thickness 100 μm, manufactured by Teijin DuPont Co., Ltd., Q65A) film was used as the base film.

[1] Formation of inorganic layer (X) An inorganic layer of aluminum oxide was formed using a reactive sputtering apparatus. Specific film forming conditions are shown below.
The vacuum chamber of the reactive sputtering apparatus was evacuated to an ultimate pressure 5 × 10 ^-4 Pa by an oil rotary pump and a turbo molecular pump. Next, argon was introduced as a plasma gas, and power of 2000 W was applied from a plasma power source. A high-purity oxygen gas was introduced into the chamber, the film formation pressure was adjusted to 0.3 Pa, and the film was formed for a certain period of time to form an aluminum oxide inorganic layer. The obtained aluminum oxide film had a thickness of 40 nm and a film density of 3.01 g / cm ³ .

[2] Formation of organic layer (Y, Z) The organic layer is formed by two methods: a film formation method (organic layer Y) by solvent coating under normal pressure and a film formation method (organic layer Z) by flash vapor deposition under reduced pressure. Done using the street. Specific film formation contents are shown below.
Film formation of organic layer (Y) 9 g of tripropylene glycol diacrylate (TPGDA, manufactured by Daicel Cytec) as photopolymerizable acrylate, and 0.1 g of photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907), methyl ethyl ketone It was dissolved in 190 g to obtain a coating solution. This coating solution was applied onto a base film using a wire bar, and a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge with an oxygen concentration of 0.1% or less, The organic layer Y was formed by irradiating ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² . The film thickness was about 500 nm.

Film formation of organic layer (Z) 9.7 g of butylethylpropanediol diacrylate (BEPGA, manufactured by Kyoeisha Chemical Co., Ltd.) and 0.3 g of a photopolymerization initiator (Lamberti spa, EZACURE-TZT) were mixed as a photopolymerizable acrylate. A vapor deposition solution was used. This vapor deposition solution was vapor-deposited on the substrate by a flash vapor deposition method under the condition that the internal pressure of the vacuum chamber was 3 Pa. Then the conditions of the same degree of vacuum, thereby forming an organic layer Z and an irradiation dose of 2J / cm ^2. The film thickness was about 1200 nm. The organic layer Z was formed using an organic / inorganic laminated film forming apparatus Guardian 200 (manufactured by Vytex Systems).

[3] Production of gas barrier film The gas barrier film was produced by sequentially forming the inorganic layer and the organic layer on the base film according to the constitution of each sample described in Table 1. The production method was performed in the following two ways.
[3-1] Method of repeating organic layer formation by solvent coating and inorganic layer formation under reduced pressure (Lamination A)
Organic layers and inorganic layers were alternately laminated on the substrate. When laminating an inorganic layer on top of an organic layer, the organic layer is formed by solvent application, and then placed in a vacuum chamber and depressurized, and after maintaining for a certain time in a state where the degree of vacuum is 10 ⁻³ Pa or less, Was deposited. When the organic layer was laminated on the inorganic layer, the organic layer was formed by solvent coating immediately after the inorganic layer was formed.
[3-2] Method for consistently forming an organic layer and an inorganic layer under reduced pressure (Lamination B)
The organic layer and the inorganic layer were laminated | stacked using the above-mentioned organic-inorganic laminated film-forming apparatus Guardian200. In this apparatus, both the organic layer and the inorganic layer are formed in a reduced pressure environment, and the organic and inorganic layer forming chambers are connected. Therefore, it is possible to continuously form the film in a reduced pressure environment. Therefore, it is not released to the atmosphere until the barrier layer is completed.

Preparation of organic EL element (Comparative Example 1)
[1] Production of Bottom Emission Type Organic EL Element Substrate A conductive glass substrate having an ITO film (surface resistance value 10Ω / □) was washed with 2-propanol and then subjected to UV-ozone treatment for 10 minutes. The following organic compound layers were sequentially deposited on this substrate (anode) by vacuum deposition.
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
Finally, 1 nm of lithium fluoride and 100 nm of metal aluminum were sequentially deposited to form a cathode, and a 3 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.

[2] Installation of gas barrier film on organic EL element Using a thermosetting adhesive (Epotec 310, Daizonitomoly Co., Ltd.), the gas barrier film and the organic EL element substrate are disposed on the side of the organic EL element. Then, the adhesive was cured by heating at 65 ° C. for 3 hours. 20 organic EL elements (Sample Nos. 201 to 203) sealed in this way were produced.

(Comparative Example 2)
[1] Production of Top Emission Type Organic EL Element Substrate A conductive glass substrate having an ITO film (surface resistance value 10Ω / □) was washed with 2-propanol, and then subjected to UV-ozone treatment for 10 minutes. The following organic compound layers were sequentially deposited on this substrate (anode) by vacuum deposition.
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
(Electron injection layer)
Lithium fluoride: thick film 1nm
(Transparent cathode and protective layer)
Silver: 10 nm in thickness and 100 nm of ITO were sequentially deposited thereon to form a transparent cathode, and a 3 μm thick silicon nitride film was attached thereon by a parallel plate CVD method to produce an organic EL device.

[2] Installation of Gas Barrier Film on Organic EL Element In the same manner as in Comparative Example 1, the gas barrier film was bonded to the organic EL element to prepare 20 organic EL elements (Sample Nos. 301 to 303).

Example 1
In Comparative Example 1, the glass substrate was replaced with the following substrate in the same manner, and 20 organic EL elements (Sample Nos. 401 to 403) were produced.
Preparation of substrate Glass substrate (thickness: 400 μm), polyethylene naphthalate (PEN, thickness 100 μm, manufactured by Teijin DuPont Co., Ltd., Q65A) film, thermosetting adhesive (Epotech 310, Daizonichi Mori Co., Ltd.) The adhesive was cured by heating at 65 ° C. for 3 hours. The obtained PEN film / glass substrate laminate was immersed in a hydrofluoric acid solution and pulled up when the glass was etched to a thickness of about 200 μm.

(Example 2)
In Comparative Example 1, the glass substrate was replaced with the following substrate in the same manner, and 20 organic EL elements (Sample Nos. 501 to 503) were produced.
Preparation of substrate On a glass substrate (thickness: 400 μm), an epoxy resin was applied to a thickness of 0.1 mm, and cured by heating at 150 ° C. for 1 hour. The obtained epoxy resin layer / glass substrate laminate was immersed in a hydrofluoric acid solution and pulled up when the glass was etched to a thickness of about 200 μm.

(Example 3)
In Comparative Example 2, the glass substrate was replaced with that used in Example 1, and the others were carried out in the same manner to produce organic EL elements (Sample Nos. 601 to 603) each for 20 elements.

Example 4
In Comparative Example 2, the glass substrate was replaced with that used in Example 2, and the others were carried out in the same manner to produce 20 organic EL elements (Sample Nos. 701 to 703).

(Example 5)
In Comparative Example 1, the glass substrate was replaced with the following substrate in the same manner, and 20 organic EL elements (Sample Nos. 801 to 803) were produced.
Substrate adjustment A glass substrate (thickness: 400 μm) and a circularly polarizing film (thickness: 280 μm, manufacturer: Bikan Imaging Co., Ltd.) are attached using a thermosetting adhesive (Epotech 310, Daizonichi Mori Co., Ltd.) Combined and heated at 65 ° C. for 3 hours to cure the adhesive. The obtained circularly polarizing film / glass substrate laminate was dipped in a hydrofluoric acid solution and pulled up when the glass was etched to a thickness of about 200 μm.

(Example 6)
In Comparative Example 1, the glass substrate was replaced with the following substrate in the same manner, and 20 organic EL elements (sample Nos. 901 to 903) were produced.
Preparation of substrate A glass substrate (thickness: 400 μm) and a light diffusion film (thickness 100 μm, manufactured by Fuji Film, UA film) are bonded together using a thermosetting adhesive (Epotech 310, Daizonichi Mori Co., Ltd.) The adhesive was cured by heating at 65 ° C. for 3 hours. The obtained light diffusing film / glass substrate laminate was immersed in a hydrofluoric acid solution and pulled up when the glass was etched to a thickness of about 200 μm.

  About the obtained sample, when a glass of 2 cm square size was dropped from a height of 50 cm onto a concrete floor to determine whether the glass was broken, in the organic EL elements of Comparative Examples 1 and 2, the glass was broken. In the organic EL elements of Examples 1 to 6, the glass was not broken.

Moreover, when the thickness unevenness was measured according to the following method for the organic EL elements of Comparative Examples 1 and 2 and Examples 1 to 6, the organic EL elements of Comparative Examples 1 and 2 had a thickness unevenness of 100 μm or more. As for the organic EL element of Examples 1-6, it was confirmed that thickness nonuniformity is 50 micrometers or less.
(Thickness unevenness measurement method)
The average thickness of four corners of an organic EL element having a size of 2 cm square (on the diagonal line of the organic EL element and located at a position of 0.1 mm from the corner) and the thickness at the point where the two diagonal lines intersect The difference was regarded as uneven thickness.

 Even when the acrylate used in the organic layer was replaced with the bisphenol acrylate compound exemplified above, the same effect was obtained.

  The manufacturing method of the present invention has an advantage that the handling property at the time of manufacture of the device manufacturer is improved and the yield is improved.

FIG. 1 is a schematic view showing an example of a light emitting device or a display device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin film 2 Glass substrate 3 Light emitting device laminated body or display device laminated body 4 Gas barrier film

Claims (15)

A light-emitting element or display element comprising a resin film or resin layer, a glass substrate, a light-emitting device laminate or a display device laminate, and a gas barrier film in that order. The light emitting element or display element of Claim 1 in which a resin film or a resin layer has a circularly-polarizing function. The light emitting element or display element of Claim 1 in which a resin film or a resin layer has a light-diffusion function. The light emitting element or display element of any one of Claims 1-3 whose thickness of a glass substrate is 100 micrometers-300 micrometers. The light emitting element or display element of any one of Claims 1-4 which has an contact bonding layer between a light emitting device laminated body or a display device laminated body, and a gas barrier film. The light emitting element or display element of any one of Claims 1-5 in which a gas barrier film has an contact bonding layer. The light emitting element or display element of any one of Claims 1-6 which has an contact bonding layer between a resin film and a glass substrate. The light emitting element or display element of any one of Claims 1-7 whose thickness of a resin film or a resin layer is 10-1000 micrometers. The light emitting element or display element of any one of Claims 1-8 which has a smooth layer between a glass substrate and a light emitting device laminated body or a display device laminated body. The light emitting element or display element of any one of Claims 1-9 whose thickness of the said smooth layer is 0.5-10 micrometers. The light emitting element or display element of any one of Claims 1-10 whose thickness nonuniformity of a glass substrate is 100 micrometers or less. The light-emitting element or display element according to any one of claims 1 to 11, wherein the gas barrier film has at least one organic region and at least one inorganic region on the base film. It is a manufacturing method of the light emitting element or display element of any one of Claims 1-12, Comprising: After bonding a resin film and a glass substrate, after etching, a light emitting device laminated body or a display device laminated body The manufacturing method characterized by providing. A light emitting device or a display device manufactured by the manufacturing method according to claim 13. The light emitting element or the display element according to claim 1, wherein the light emitting element or the display element is an organic EL element.

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