JP2005319678A - Laminate, light emitting element and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic EL element more excellent in water vapor barrier properties and scratch resistance than a conventional one and excellent in emission takeout efficiency. <P>SOLUTION: This laminate is composed of a sealing film, which is formed by laminating at least one inorganic film and at least one organic film, and a transparent resin base material, wherein the organic film is a film formed using at least a metal or a semimetal elemental substance or a compound thereof and an alicyclic structure-containing polymer as a raw material. The light emitting element is constituted by successively laminating a lower electrode layer, a light emitting material layer, an upper electrode layer and a sealing layer on a transparent substrate, wherein the sealing layer is the sealing film formed by laminating at least one inorganic film and at least one organic film and the organic film is the film formed using at least a metal or a semimetal alone or a compound thereof and an alicyclic structure-containing polymer as the raw material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a light-emitting element such as a laminate that blocks oxygen, water vapor, and the like, an organic electroluminescence element (hereinafter, abbreviated as “organic EL element”), and use thereof.

  A gas barrier film in which a gas barrier layer is formed on a transparent resin film substrate is well known as a packaging material for food and medicine. Since this gas barrier film is excellent in its thinness, lightness and flexibility, it attracts attention as a base material for electronic devices. Particularly for liquid crystal and organic electroluminescence display substrates, resin film substrates are expected for wall-mounted TV and electronic paper applications. In base materials for electronic devices, gas barrier properties, particularly water vapor barrier properties, which are higher than those required for conventional packaging materials are required, and the development of various gas barrier layers has been reported.

As the gas barrier layer, single layer films of inorganic oxides such as SiO ₂ and Al ₂ O ₃ have been mainly used. When the single layer inorganic oxide film is thin, the gas barrier property is not sufficiently exhibited. However, when the film thickness is increased in order to sufficiently exhibit the gas barrier property, the internal stress increases and the film warps, so that the film may be cracked and the gas barrier property may be lowered.

Patent Document 1 or Patent Document 2 describes that a high gas barrier property is obtained by a laminate of an inorganic film and a resin film such as polyarylate or polyacrylate. According to this technique, it is reported that there is an advantage that cracks are hardly generated in the inorganic film because the internal stress can be relieved by inserting the organic film between the inorganic film and the inorganic film. However, as a result of our study, it was confirmed that the adhesion between the resin film and the inorganic film was low and it was easy to peel off. Due to this peeling, defects are likely to occur in the inorganic film, and as a result, the gas barrier property may be lowered. Furthermore, since a resin film such as polyarylate or polyacrylate has a high water absorption rate, when forming an inorganic film, water vapor or the like is released from the resin film, which may reduce the density of the inorganic film. In addition, the number of laminated layers of the inorganic film and the resin film such as polyarylate or polyacrylate must be stacked in a multilayer of 8 or more, which is insufficient in terms of manufacturing efficiency.
Patent Document 3 describes that in a gas barrier laminate of an inorganic film and an organic film, a hydrocarbon polymer having an alicyclic structure is used for the organic film. Since this polymer has a low water absorption rate and very little gas emission, it seems to be suitable as an organic film of the laminate. However, as a result of our study, the solution described in Patent Document 3 sometimes has insufficient adhesion between the hydrocarbon polymer having an alicyclic structure and the inorganic film.

On the other hand, organic EL elements are expected to be applied as electronic displays and light sources as high-efficiency light-emitting elements. Examples of organic EL elements include a structure in which a hole transport layer and a light emitting material layer are formed between a hole injection electrode serving as an anode and an electron injection electrode serving as a cathode (SH-A structure), and a hole injection electrode Having a two-layer structure (SH-B structure) in which a light emitting material layer and an electron transport layer are formed between an electron injection electrode and an electron injection electrode, or a hole transport layer between a hole injection electrode and an electron injection electrode And a three-layer structure having a structure (DH structure) in which a light emitting material layer and an electron transport layer are formed.
In any structure, the organic EL element has a hole injected from the hole injection electrode (anode) and an electron injected from the electron injection electrode (cathode), the interface between the light emitting material layer and the hole (or electron) transport layer, And it is the principle of recombination within the light emitting material layer to emit light. Therefore, compared with an inorganic EL element whose light emission mechanism is collision erection type light emission, the organic EL element has a feature that it can emit light at a low voltage, and is very promising as a light emitting element in the future.

  FIG. 1 shows a configuration example of a typical EL element. The organic EL element shown in FIG. 1 includes a transparent substrate 16, a lower electrode layer 54, a light emitting material layer 62, and an upper electrode layer 55. The conventional organic EL element has a method of emitting light emitted from the light emitting material layer 62 from the transparent substrate 16 side (bottom emission method). However, since a thin film transistor is installed on the transparent substrate side, the light emission area is small. Become. Therefore, recently, a method of emitting light from the opposite side of the transparent substrate 16 as viewed from the light emitting material layer 62 (top emission method) has attracted attention because a sufficient light emission area can be obtained.

However, since the organic EL element uses a material having a low work function as a cathode for improving characteristics, corrosion and oxidation are likely to occur due to reaction with moisture and oxygen in the air. Such deterioration of the cathode significantly grows a non-light emitting portion called a dark spot existing in the light emitting material layer, which causes deterioration of characteristics over time in the organic EL element.
Further, not only the cathode but also organic materials used for the light emitting material layer, the transport layer, and the like generally cause structural changes due to reaction with moisture and oxygen, which similarly causes the growth of dark spots. .
Therefore, in order to increase the durability and reliability of the organic EL element, the entire organic EL element is used in order to prevent the reaction between the organic material used in the cathode, the light emitting material layer, the transport layer, etc., moisture and oxygen. Must be sealed.
Therefore, many studies have been conducted on the sealing of organic EL elements.

For example, Patent Document 4 discloses a method of forming Si ₃ N ₄ , a diamond-like carbon film, or the like on the outer surface of an organic EL element by an ECR plasma CVD method. According to this, it is described that the oxidation of the electron injection electrode (cathode) can be prevented and the moisture resistance of the organic EL element can be improved. However, in the above materials, it is necessary to increase the film thickness in order to improve the moisture resistance. As a result, the internal stress increases, the film is liable to crack, and the moisture resistance may decrease.
Patent Document 5 discloses a method of sealing an organic EL element with a laminated structure of an organic material and silicon nitride oxide. According to this, it is possible to form a film thickness that can completely suppress the growth of dark spots on top of the organic EL element, and it is dense and can prevent entry of moisture, oxygen, etc. from the outside. It is described that a highly reliable organic EL can be provided by providing the portion. However, if the chemical structure and the film formation method are not limited, the adhesion between the organic substance and silicon nitride oxide is extremely low, and defects at the interface due to peeling may occur, resulting in a reduction in moisture resistance.

  Moreover, the present applicant has proposed a sealing film for an organic EL element made of a perfluoroolefin decomposition polymer in Patent Document 6. According to this, deterioration of the organic EL element can be suppressed by ambient oxygen and moisture, and the light extraction efficiency of the element can be effectively improved, and the element can be reduced in size and thickness. It is described. However, the sealing property is insufficient to apply to the organic EL device using only the polymer, and further improvement is required.

JP 2003-206361 A JP 2003-48271 A JP 2002-234103 A JP-A-10-261487 JP 2002-25765 A JP 2002-056771 A

  An object of the present invention is to provide a laminate having excellent water vapor barrier properties and scratch resistance, and further, a light emitting device such as an organic EL device having excellent water vapor barrier properties and scratch resistance and a long light emission lifetime, and the like. It is providing the apparatus provided with.

  As a result of diligent research to solve the above-mentioned problems, the present inventors are a sealing film formed by laminating an inorganic film and an organic film, and the organic film is a film made of a metal compound and a specific polymer as raw materials. It was found that the above-mentioned object can be achieved by using a material, and the present invention has been completed based on this finding.

Thus, according to the present invention,
(1) A laminate composed of a sealing film formed by laminating at least one inorganic film and at least one organic film, and a transparent resin base material, wherein the organic film is at least a metal or a semimetal simple substance or A laminate which is a film made of a compound and an alicyclic structure-containing polymer as raw materials.
(2) A light emitting device in which a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked, and the sealing layer is the stacked body.
(3) A light emitting device in which a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially laminated, and the substrate is the laminate.
(4) A sealing in which a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked, and the sealing layer is a stack of at least one inorganic film and at least one organic film. A light-emitting element, which is a film, and wherein the organic film is a film using at least a metal or semimetal simple substance or compound and an alicyclic structure-containing hydrocarbon polymer as raw materials.
(5) A light emitting device in which a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked, and the substrate and the sealing layer are the stacked body.
(6) A substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked, the substrate is the stacked body, and the sealing layer includes at least one inorganic film and at least one sealing layer. A light-emitting element, which is a sealing film formed by laminating organic films, wherein the organic film is a film using at least a metal or semimetal simple substance or compound and an alicyclic structure-containing hydrocarbon polymer as raw materials.
(7) A light-emitting element having a light transmittance of 80% or more in the wavelength range of 400 nm to 800 nm when not emitting light.
(8) A planar light source including the light emitting element.
(9) A dot matrix display device including the light emitting element.
(10) A liquid crystal display device comprising the light emitting element as a backlight.
Are provided respectively.

Since the laminate of the present invention is excellent in water vapor barrier properties and scratch resistance, it is not only suitable as a packaging material, but also a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, etc. It is useful as a sealing layer for light-emitting elements such as organic EL elements used in the above.
In addition, the light-emitting element of the present invention has a long light emission lifetime and is excellent in water vapor barrier properties and surface scratch resistance, and thus is useful as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like. is there.

  The laminate of the present invention is a laminate comprising a sealing film formed by laminating at least one inorganic film and at least one organic film, and a transparent resin base material, and the organic film is at least a metal or a semi-solid. It is a film made of a metal simple substance or compound and an alicyclic structure-containing polymer as raw materials.

  The alicyclic structure-containing polymer as a raw material of the organic film constituting the laminate of the present invention is a polymer having a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, a polymer having a cycloalkane structure is preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the mechanical strength of the film. The properties such as heat resistance are highly balanced and suitable. The proportion of the repeating unit containing the alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected, but is preferably 30% by weight or more, more preferably 50% by weight or more, Especially preferably, it is 70 weight% or more, Most preferably, it is 90 weight% or more. It is preferable from a viewpoint of transparency and heat resistance that the ratio of the repeating unit which has an alicyclic structure in the polymer which has an alicyclic structure exists in this range.

  Specific embodiments of the alicyclic structure-containing polymer include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic polymer. Examples thereof include hydrocarbon polymers and hydrogenated products thereof. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

  The metal or semimetal simple substance or compound as the raw material of the organic film constituting the laminate of the present invention is a metal or semimetal simple substance or compound as the raw material of the inorganic film constituting the laminate of the present invention. In particular, those that produce gas barrier properties when a film is formed are preferred. For example, a simple substance or compound of metals or semimetals of Group 4 to Group 16 of the Periodic Table can be mentioned, and compounds of Group 4, 13 and 14 are preferred. More preferred are organic compounds and inorganic compounds containing at least one selected from the group consisting of titanium atoms, aluminum atoms and silicon atoms, and organic compounds containing at least one selected from the group consisting of titanium atoms, aluminum atoms and silicon atoms Particularly preferred. Organic compounds containing at least one selected from the group consisting of titanium atoms, aluminum atoms, and silicon atoms are less likely to form flexible films than inorganic compounds, so the internal stress is small and sealing properties (gas barrier properties) are reduced. This has the advantage that cracks that cause the above are difficult to form.

Examples of the organic compound containing a titanium atom include titanium tetraethoxide, titanium tetramethoxide, titanium isopropoxide, tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, and the like.
Examples of the organic compound containing an aluminum atom include tri (isopropoxide) aluminum, tri (ethoxy) aluminum, aluminum butoxide, and aluminum phenoxide. In addition, an organic complex compound of aluminum, for example, aluminum acetylacetonate, aluminum aluminum acetoacetate, aluminum methacrylate, aluminum pentanedionate, and the like can be given.
Examples of organic compounds containing silicon atoms include organic monosilane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane; organic polysilane compounds such as hexamethyldisilane, 1,2-diphenyltetramethyldisilane, and hexamethoxydisilane; And organic siloxane compounds such as methyldisiloxane and tetramethyldisiloxane; organic silazane compounds such as tetramethyldisilazane and hexamethyldisilazane;
Examples of the inorganic compound include oxides, nitrides, nitrogen oxides, and the like, and oxides and nitrides are preferable. Specifically, examples of the oxide include SiO, SiO ₂ , Al ₂ O ₃ , TiO, TiO ₂ , and Ti ₃ O ₅ ; and examples of the nitride include Si ₃ N ₄ , AlN, and TiN.

The organic film is not particularly limited by the formation method. Examples thereof include a coating method, a vapor deposition method, a sputtering method, a CVD (chemical vapor deposition) method, and the like.
In the coating method, a particulate metal or metalloid simple substance or compound is added to an alicyclic structure-containing polymer solution, and a coating obtained by mixing and dispersing is applied to form a film. The particle size of the fine particles to be mixed and dispersed in the polymer solution is not particularly limited as long as the optical properties are not impaired, and is preferably 1 μm or less, more preferably 50 nm or less.
In a method using a so-called dry process, such as a vapor deposition method, a sputtering method, or a CVD method, a metal or metalloid simple substance or compound and an alicyclic structure-containing polymer are evaporated and deposited on a substrate. To do.

Among the CVD methods, the plasma CVD method is the simplest and well-known method. The plasma CVD method is conventionally known, for example, as described in JP-A-9-237783. As an apparatus used for the plasma CVD method, a parallel plate type CVD apparatus is generally used, but a microwave CVD apparatus, an ECR-CVD apparatus, and a high-density plasma CVD apparatus (helicon wave plasma, inductively coupled plasma, etc. are used). it can.
The raw material metal or metalloid simple substance or compound and the alicyclic structure-containing polymer are introduced into the chamber after exhausting the pressure in the chamber of the CVD apparatus to 0.1 Pa or less.

When the raw material is solid, it is introduced into the chamber by heating, evaporating using an electron beam, or applying high voltage to cause sputtering. When the raw material is a liquid, it is evaporated using a vapor pressure difference, or a container containing the raw material is heated and evaporated with a mantle heater or the like and introduced into the chamber. When the raw material is a gas, it is introduced into the chamber as it is.
After introducing the raw material into the chamber, a direct current or alternating current (10 kHz to 100 MHz) voltage is applied at an output of about 10 W to about 10 kW to generate plasma between the electrodes, thereby forming a sealing film on a predetermined substrate. . The substrate temperature at that time is 500 ° C. or less, and when the transparent substrate is a resin having low heat resistance, it is preferable not to heat. The pressure in the system during film formation is preferably 1 × 10 ⁻² to 1 × 10 ⁴ Pa.
For example, a CVD method is used to evaporate a norbornene-based polymer as a raw material alicyclic structure-containing polymer and silazane as a raw material metal compound, and generate plasma in a vacuum chamber to form a transparent resin substrate. Precipitate to form an organic film.

  The average thickness of the organic film is preferably 1 nm to 5 μm, more preferably 5 to 2 μm. If the organic film is too thin, the adhesion to the inorganic film and the gas barrier property may be reduced. Conversely, if the organic film is too thick, the transparency may be reduced.

The volume composition ratio M / C of metal atoms or metalloid atoms M and carbon atoms C contained in the organic film is preferably in the range of 0.01 to 0.99. When the value of M / C is within this range, it is easy to obtain a laminate having excellent adhesion with the inorganic film. The measuring method of M / C is based on X-ray electron spectroscopic analysis. The water absorption rate of the organic film is preferably 0.1% or less. By using an organic film having a water absorption rate in this range, the denseness of the inorganic film is increased and the gas barrier property of the laminate is increased.
The value of M / C can be adjusted by changing the supply ratio of the metal or metalloid simple substance or compound and the alicyclic structure-containing polymer. The supply amount here means the evaporation rate when the raw material is solid, and the evaporation flow rate when it is liquid or gas.

  The inorganic film constituting the laminate of the present invention is made of an inorganic compound having gas barrier properties. The inorganic compound is not particularly limited as long as gas barrier properties can be imparted. As a raw material of the inorganic film, a simple substance or compound of a metal or a semimetal such as Si, Mg, Ti, Al, In, Sn, Zn, W, Ce, and Zr is preferable. As the compound, oxide, nitride, nitride oxide, and sulfide are preferable, and oxide, nitride, and nitride oxide are particularly preferable.

  Examples of oxides include aluminum oxide, silicon dioxide, silicon oxynitride, or mixtures thereof, ITO (indium tin oxide), IZO (indium zinc oxide), AZO (aluminum zinc oxide), zinc oxide, zinc sulfide, ICO (Indium cerium oxide), titanium oxide, etc. are mentioned. Examples of the nitride include silicon nitride. Among these, silicon dioxide or silicon oxynitride is preferable. An inorganic film formed using silicon dioxide or silicon oxynitride is transparent and can have a high gas barrier property.

The average thickness of the inorganic film is preferably 5 to 500 nm, more preferably 10 to 250 nm. If the average thickness of the inorganic film is too thin, the gas barrier property may be insufficient. On the other hand, if the inorganic film is too thick, the film loses flexibility and is likely to crack.
The crystalline state of the inorganic film is preferably a uniform amorphous structure that does not include a columnar structure or a granular structure. When a columnar structure or a granular structure is included, the crystal grain boundary becomes a gas molecule diffusion path, and the gas barrier property may be lowered.

  The inorganic film is not particularly limited by the formation method. In terms of efficiently forming an inorganic film having a high film density, vacuum deposition, sputtering, and CVD are preferred, vacuum deposition and CVD are more preferred, and damage to organic films and transparent resin substrates is further preferred. In particular, a vacuum vapor deposition method and a CVD method using arc discharge plasma are particularly preferable in that the film density can be increased. When arc discharge plasma is used, evaporated particles having appropriate energy are generated, and a high-density film can be formed.

The vacuum deposition method is a method of forming a deposited film by heating and evaporating a deposition material by a method such as resistance heating, electron beam heating, laser beam heating, arc discharge, etc. in a vacuum of about 10 ⁻² to 10 ⁻⁵ Pa. . Further, in the sputtering method, a cation such as Ar ⁺ accelerated by glow discharge or the like is bombarded on a target (vapor deposition material) in a vacuum of about ¹ to 10 ⁻¹ Pa in which an inert gas such as argon exists. In this method, the vapor deposition material is sputter evaporated to form a vapor deposition film on the surface of the resin film substrate. Examples of the evaporation method include DC (direct current) sputtering, RF (radio frequency) sputtering, magnetron sputtering, and bias sputtering. The ion plating method is a vapor deposition method in which the above vacuum vapor deposition method and the sputtering method are combined. By this method, in a vacuum of about 1 to 10 ⁻¹ Pa, evaporated atoms released by heating can be ionized and accelerated in an electric field to form a thin film in a high energy state.
The CVD method uses a metal or metalloid compound as a vapor deposition material in the CVD method in the formation of the organic film, or a metal or metalloid simple substance and a substance containing an oxygen atom, a nitrogen atom, or a sulfur atom. It is a method of using them in combination, evaporating them, reacting them as necessary, and depositing them on a substrate to form a film.
Among these inorganic film forming methods, when a wide film is formed, the sputtering method is preferable in that the film thickness uniformity in the width direction, adhesion, productivity, and yield can be improved.

  The transparent resin base material which comprises this invention laminated body is a film-form base material formed from the transparent resin which has transparency and flexibility. Examples of the transparent resin include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products containing these alicyclic structures. Polymers: Chain olefin polymers such as polyethylene and polypropylene; Polycarbonate polymers; Polyester polymers; Polysulfone polymers; Polyethersulfone polymers; Polystyrene polymers; Polyvinyl alcohol polymers, Cellulose acetates Examples thereof include a polymer, a polyvinyl chloride polymer, and a polymethacrylate polymer. Among these, an alicyclic structure-containing polymer is particularly preferable from the viewpoints of transparency, low hygroscopicity, dimensional stability, lightness, and the like.

The molecular weight of the transparent resin constituting the transparent resin substrate is a polyisoprene or polystyrene equivalent weight average molecular weight measured by gel permeation chromatography using cyclohexane (toluene or tetrahydrofuran when the resin is not dissolved) as a solvent. (Mw) is usually 5,000 to 100,000, preferably 8,000 to 80,000, more preferably 10,000 to 50,000. When Mw is in such a range, the mechanical strength and moldability of the substrate are highly balanced, which is preferable.
Moreover, the glass transition temperature of the said transparent resin becomes like this. Preferably it is 80-280 degreeC, More preferably, it is 100-250 degreeC. A film-like substrate formed of a transparent resin having a glass transition temperature in such a range is excellent in durability without being deformed or stressed even when used at a high temperature.

The average thickness of the transparent resin substrate is preferably 30 to 300 μm, more preferably 40 to 200 μm, from the viewpoint of mechanical strength and the like.
Moreover, it is preferable that the thickness fluctuation | variation of a transparent resin base material is less than 3% of the said average thickness over the base material full width. When the thickness variation of the substrate is in the above range, the adhesion and surface smoothness of the sealing layer can be improved.

  The transparent resin substrate preferably has a volatile component content of 0.1% by weight or less, and more preferably 0.05% by weight or less. When the content of the volatile component is in the above range, the dimensional stability of the laminate is improved, and the thickness unevenness of the laminated inorganic film or organic film can be reduced.

  The transparent resin substrate preferably has a saturated water absorption of 0.01% by weight or less, and more preferably 0.007% by weight or less. When the saturated water absorption is high, the adhesion between the inorganic film or the organic film and the transparent resin substrate is lowered, and delamination is likely to occur during long-term use. Furthermore, the time required for evacuation due to moisture released from the base material may change, or the inorganic film or the organic film may be altered, resulting in a decrease in productivity and yield. Based on JIS K7209, the saturated water absorption rate of the base material was measured by measuring the weight of the base material that had been dried in an oven, immersing it in distilled water, wiping the moisture, and comparing it with the weight before immersion. Then, the water absorption is calculated from the weight increase.

  The transparent resin base material is an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a dispersant, a chlorine scavenger, a flame retardant, a crystallization nucleating agent, an antiblocking agent, if necessary. Known antifogging agents, release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, antibacterial agents and other resins, thermoplastic elastomers, etc. An additive can be contained in the range which does not impair the effect of invention. These additives are each usually blended in an amount of 0 to 5 parts by weight, preferably 0 to 3 parts by weight, per 100 parts by weight of the transparent resin.

  A transparent resin base material is not restrict | limited by the manufacturing method, For example, it can obtain by the solution casting method or the melt extrusion method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the transparent resin substrate and the thickness unevenness can be reduced. Further, examples of the melt extrusion method include a method using a die and an inflation method, but a method using a die, particularly a T die, is preferable in terms of excellent thickness accuracy and productivity.

  The transparency of the transparent resin substrate used in the present invention is preferably 85% or more, more preferably 90% or more, as the total light transmittance at a thickness of 3 mm. If the transparency is too small, it may be difficult to use for optical purposes.

As the transparent resin base material, one having one or both surfaces subjected to surface modification treatment may be used. By performing the surface modification treatment, the adhesion with an organic film or an inorganic film can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.
Examples of the energy beam irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment, particularly corona discharge treatment is preferable.
As chemical treatment, it may be immersed in an aqueous oxidizing agent solution such as potassium dichromate solution or concentrated sulfuric acid and then thoroughly washed with water. Shaking in the immersed state is efficient, but the surface dissolves or transparency decreases when treated for a long period of time, so it is necessary to adjust the treatment time according to the reactivity and concentration of the chemical used. is there.

The laminate of the present invention has a structure in which one or two or more organic films and inorganic films are alternately laminated on one side or both sides of the transparent resin substrate. The number of organic or inorganic films may be the same, or one of them may be one more. FIG. 2 is a cross-sectional view showing an example of the laminate 100 of the present invention. On the transparent resin substrate 12, a sealing film 42 composed of an inorganic film 33, an organic film 23, and an inorganic film 34 is laminated.
The film in contact with the transparent resin substrate may be an organic film or an inorganic film, but if the organic film is in contact with the resin film substrate, the surface of the resin film substrate may be uneven. Since the surface of the organic film is smoothed by forming the organic film thereon, the inorganic film formed on the organic film is preferable because it becomes a dense and smooth film without defects and has high gas barrier properties. In this embodiment, even if the resin film substrate is subjected to external force, it is relaxed by the organic film, so that the inorganic film is not easily cracked, and high gas barrier properties are maintained for a long time.

  Next, the light emitting device of the present invention will be described. FIG. 3 is a cross-sectional view showing an example of the first embodiment of the light emitting device of the present invention. The light emitting device 200 according to the first embodiment of the present invention comprises a substrate 16, a lower electrode layer 54, a light emitting material layer 62, an upper electrode layer 55 and a sealing layer 105, which are sequentially laminated. It is a laminate.

  The substrate 16 used in the light-emitting device of the present invention has a light transmittance in the visible region of 400 to 700 nm of 50% or more, is smooth, and does not change when an electrode or each layer of the device is formed. Is preferred. Examples of such a substrate include a glass plate and a polymer film. The average thickness of the substrate is usually 30 μm to 3 mm, preferably 50 to 300 μm.

Examples of the material constituting the upper electrode layer 55 used in the light emitting element of the present invention include a material for emitting light from the upper electrode layer, and specifically, a conductive metal oxide, a translucent metal, or a material thereof. A laminated body is mentioned. Specifically, indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive glass (NESA etc.), gold, platinum Silver, copper, etc. are used, and among them, ITO, indium / zinc / oxide, and tin oxide are preferable. Further, as the upper electrode layer, an organic transparent conductive film such as polyaniline or a derivative thereof or polythiophene may be used.
The average thickness of the upper electrode layer can be appropriately selected in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 100 to 500 nm.
In the light emitting device of the present invention, it is convenient that the upper electrode layer is transparent or translucent because the emission efficiency of light emission is good. Examples of the method for forming the upper electrode layer include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.

There is no restriction | limiting in particular as a material which comprises the light emitting material layer 62 used for the light emitting element of this invention, The well-known thing can be used as a light emitting material in a conventional organic EL element. Specific examples of such light-emitting materials include fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, styrylbenzene compounds, distyrylpyrazine derivatives, and aromatic dimethylidine compounds. Etc.
The average thickness of the light-emitting material layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, the average thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. .
In the light emitting device of the present invention, two or more kinds of light emitting materials may be mixed and used in the light emitting material layer, or two or more light emitting material layers may be laminated. Examples of the method for forming the light emitting material layer include a vacuum deposition method and a casting method.

The material constituting the lower electrode layer 54 used in the light emitting device of the present invention is preferably a material having a small work function, in order to reflect the emitted light from the light emitting material layer toward the lower electrode layer and to direct it toward the sealing layer. More preferably, it is a mirror body. Specifically, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And two or more alloys thereof, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite An intercalation compound or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The lower electrode layer may have a laminated structure of two or more layers. Examples of the method for forming the lower electrode layer include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
The average thickness of the lower electrode layer can be appropriately selected in consideration of electric conductivity and durability, but is usually 10 nm to 10 μm, preferably 100 to 500 nm.

The light emitting device of the present invention may have other layers in addition to the transparent substrate 16, the lower electrode layer 54, the light emitting material layer 62, the upper electrode layer 55, and the sealing layer 105.
Examples of the other layers include a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.
The hole injection layer is a layer provided adjacent to the lower electrode and refers to a layer having a function of improving hole injection efficiency from the lower electrode. The average thickness of the hole injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.
The hole transport layer refers to a layer having a function of transporting holes. The thickness of the hole transport layer differs depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the average thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm.
Examples of materials used for the hole injection layer and the hole transport layer include those conventionally known as hole transport compounds in organic EL devices.

The electron transport layer refers to a layer having a function of transporting electrons.
The thickness of the electron transport layer varies depending on the material used and may be selected so that the driving voltage and the light emission efficiency are appropriate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element becomes high, which is not preferable. Therefore, the average thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm.
The electron injection layer is a layer provided adjacent to the upper electrode layer and has a function of improving the electron injection efficiency from the upper electrode and has an effect of reducing the driving voltage of the element.
The average thickness of the electron injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.
Examples of materials used for the electron transport layer and the electron injection layer include those conventionally known as electron transport compounds in organic EL devices.
Examples of methods for forming these other layers include spin coating, casting, and vacuum deposition.

The sealing layer 105 of the first embodiment is the above-described laminate of the present invention. That is, the sealing layer 105 includes the transparent resin base material 12 and the sealing film 42 composed of the inorganic film 33, the organic film 23, and the inorganic film 34. By covering and closely adhering the light emitting element with the laminate of the present invention, deterioration of the light emitting material layer due to water vapor or oxygen can be prevented.
In the organic EL device of the present invention, it is preferable that a sealing layer is provided so as to cover the side surfaces of the lower electrode layer, the light emitting material layer, and the upper electrode layer, and it is more preferable to cover the transparent substrate. By providing the sealing layer as described above, moisture and gas entering from the side surface can be shielded. In FIG. 2, the transparent substrate 16 and the sealing layer 105 are sealed with an adhesive 300.

FIG. 4 is a cross-sectional view showing an example of the second embodiment of the light emitting device of the present invention. The light emitting device 201 according to the second embodiment of the present invention includes a substrate 100, a lower electrode layer 56, a light emitting material layer 63, an upper electrode layer 57, and a sealing layer 400, which are sequentially stacked. Is the body.
The lower electrode layer 56, the light emitting material layer 63, and the upper electrode layer 57 are the same as in the first embodiment. As the sealing layer 400, a layer normally used in an organic EL element is used.
The substrate 100 of the second embodiment is the above-described laminate of the present invention. By laminating an electrode layer, a light emitting material layer, and the like on the laminate of the present invention, permeation of water vapor, oxygen, and the like from the substrate side can be prevented, and deterioration of the electrode layer and the light emitting material layer can be prevented. The substrate 100 used in the light emitting device of the present invention has a light transmittance in the visible region of 400 to 700 nm of 50% or more, is smooth, and does not change when forming electrodes and each layer of the device. Is preferred. The average thickness of the substrate is usually 30 μm to 3 mm, preferably 50 to 300 μm.

In a third embodiment of the light emitting device of the present invention, a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked, and the sealing layer includes at least one inorganic film and at least one organic layer. The organic film is a film obtained by using at least a metal or semimetal simple substance or compound and an alicyclic structure-containing polymer as raw materials.
FIG. 5 shows a sectional view of an organic EL element (light emitting element) as a third embodiment.
FIG. 5 is a cross-sectional view of an example when the sealing layer 44 constituting the organic EL element 202 of the present invention is composed of a plurality of layers. The organic EL element of FIG. 5 includes a transparent substrate 14, a lower electrode layer 50, a light emitting material layer 60, an upper electrode layer 51, and a sealing layer 44. The lower electrode layer 50, The light emitting material layer 60 and the upper electrode layer 51 are sequentially laminated, and the lower electrode layer 50, the light emitting material layer 60, and the upper electrode layer 51 are sealed with a sealing layer 44. The sealing layer 44 is formed by laminating at least one inorganic film 38, 39 and at least one organic film 26, 27. The organic film includes at least a simple substance or compound of metal or metalloid, and a fat. It consists of a film made from a ring structure-containing hydrocarbon polymer.

  The sealing layer 44 of the third embodiment has the same configuration as the sealing film 42 constituting the above-described laminate 100 of the present invention. The method for forming the sealing layer and the preferred embodiment are as described above, except that the transparent resin substrate 12 is replaced with a laminate of the transparent substrate 14, the lower electrode layer 50, the light emitting material layer 60, and the upper electrode layer 51. This is the same as described in the explanation of the laminate.

In the light-emitting element of the present invention, it is preferable that the water vapor transmission rate of the sealing layer is less than 0.1g ^/ m 2 ^/ 24hr, more preferably not more than 0.09g ^/ m 2 ^/ 24hr. Thereby, sufficient sealing becomes possible and deterioration of the light emitting material is suppressed. The water vapor transmission rate can be measured using a commercially available water vapor transmission rate measuring device in accordance with the method B of JIS-K7129. In addition, when a sealing layer is a laminated body, the water vapor transmission rate of the whole laminated body is meant.
In the light emitting device of the present invention, the average thickness of the sealing layer is preferably 10 nm to 1 μm, more preferably 100 nm to 500 nm.

  FIG. 6 is a cross-sectional view showing an example of the fourth embodiment of the light emitting device of the present invention. The light-emitting element 203 of the fourth embodiment of the present invention corresponds to a combination of the first embodiment and the second embodiment. Specifically, the substrate 100, the lower electrode layer 58, the light-emitting material layer 64, the upper electrode layer. 59 and the sealing layer 105 are sequentially laminated, and both the substrate 100 and the sealing layer 105 are the above-described laminate of the present invention.

  FIG. 7 is a cross-sectional view showing an example of the fifth embodiment of the light emitting device of the present invention. The light emitting element 204 of the fifth embodiment of the present invention corresponds to a combination of the second embodiment and the third embodiment. Specifically, the substrate 100, the lower electrode layer 50, the light emitting material layer 60, the upper electrode layer. 51 and a sealing layer 44 are sequentially laminated, the substrate is the above-described laminate of the present invention, and the sealing layer is formed by laminating at least one inorganic film 38, 39 and at least one organic film 26, 27. Thus, the organic film is a film made of at least a metal or metalloid simple substance or compound and an alicyclic structure-containing hydrocarbon polymer.

  The light emitting device of the present invention preferably has a light transmittance in the wavelength range of 400 nm to 800 nm when not emitting light, preferably 80% or more, particularly preferably 90% or more. Even if the light emitting element of the present invention is provided on a windshield of an automobile or the like, the light transmittance at the time of non-light emission is high, so that the front visibility is not hindered.

  The light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

  In order to obtain a planar light source including the light emitting element of the present invention, a planar anode (upper electrode layer) and a cathode (lower electrode layer) may be disposed. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There are a method of emitting light and a method of forming either or both of the anode and the cathode in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols, and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multi-color display are possible by a method of separately coating a plurality of types of polymers having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element may be either passive drive or active drive combined with a thin film transistor using amorphous silicon or low-temperature polysilicon. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like. Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
Parts and% are based on weight unless otherwise specified.
Example 1
FIG. 2 is a cross-sectional view of the laminated body in Examples 1 to 3 of the present invention.
In Example 1, a film having an average thickness of 100 μm obtained by extruding an alicyclic structure-containing polymer (manufactured by Nippon Zeon Co., Ltd., ZEONOR 1620) was used as the transparent resin substrate 12, and SiO ₂ was formed on the substrate. An inorganic film 33 having an average thickness of 200 nm was formed by RF sputtering as a target material. Subsequently, an alicyclic structure-containing polymer (manufactured by Nippon Zeon Co., Ltd., ZEONOR 1620) is supplied with raw materials at an evaporation rate of 90 nm / min and SiO ₂ at an evaporation rate of 10 nm / min. It formed on the said inorganic film. Furthermore, an inorganic film 34 having an average thickness of 200 nm was formed on the organic film by RF sputtering using SiO ₂ as a target material, and a laminate 100 having a sealing layer 42 was obtained.

(Water absorption rate of organic film)
The laminated intermediate having a layer structure of transparent resin substrate / inorganic film / organic film obtained during the production of the laminate is placed in an oven at 60 ° C. and dried for 30 minutes, then immersed in water at 60 ° C. for 24 hours, The weight difference before and after the immersion was measured, and the ratio of the laminated intermediate to the dry weight was calculated and determined.

(Composition of organic film)
The volume ratio of Si and C was determined by measurement with an X-ray electron spectrometer.
(Water vapor transmission rate of sealing film composed of inorganic and organic films)
In accordance with JIS K7129 method B (infrared sensor method), the measurement was performed using a water vapor transmission rate meter (manufactured by MOCON, “Permatran”) in an environment of 40 ° C. and 90% RH. When measuring the water vapor transmission rate, a PET film (average thickness: 100 μm) is used as a substrate, and a laminate in which a sealing film is formed on the substrate is used as a measurement target. And the water vapor transmission rate of a sealing layer is computed by the following formula. Separately, the water vapor transmission rate of only the substrate is also measured.
Po / do = (df / Pf + ds / Ps) -1
In the above formula, Po, Pf, and Ps represent the water vapor transmission rates of the laminate, the sealing layer, and the substrate film, respectively, and do, df, and ds represent the average thicknesses of the laminate, the sealing layer, and the substrate film, respectively. Represent. The smaller the water vapor transmission rate, the better the water vapor barrier property.

(Adhesion)
The number of pieces that have not been peeled off when the surface portion of the sealing film is cut into 100 pieces by applying a cross-cut adhesive tape test in accordance with JIS D0202-1988, and the adhesive tape is applied to each cut piece and then peeled off. Count. The smaller the number of pieces, the better the adhesion. These evaluation results are shown in Table 1.

Example 2
In the formation of the organic film 23, the same procedure as in Example 1 was performed except that the evaporation rate of the alicyclic structure-containing polymer (Zeonor 1620, manufactured by Nippon Zeon Co., Ltd.) and SiO ₂ was changed to an evaporation rate of 40 nm / min. A laminate was obtained and evaluated. The evaluation results are shown in Table 1.
Example 3
In the formation of the organic film 23, the same procedure as in Example 1 was performed except that the evaporation rate of the alicyclic structure-containing polymer (Zeonor 1620, manufactured by Nippon Zeon Co., Ltd.) and SiO ₂ was changed to an evaporation rate of 90 nm / min. A laminate was obtained and evaluated. The evaluation results are shown in Table 1.

Comparative Example 1
In the formation of the organic film, lamination was carried out in the same manner as in Example 1 except that the evaporation rate of the alicyclic structure-containing polymer (Zeonor 1620, manufactured by Nippon Zeon Co., Ltd.) and SiO ₂ was changed to an evaporation rate of 0 nm / min. A body was obtained and evaluated. The evaluation results are shown in Table 1.

表中ＣＯＰはシクロオレフィンポリマーの略称であり、脂環構造含有重合体を表す。

In the table, COP is an abbreviation for cycloolefin polymer and represents an alicyclic structure-containing polymer.

(Luminescence lifetime T)
The organic EL element is continuously driven at a constant current under the condition that the initial emission luminance is 100 cd / m ² in an environment of 20 ° C. and 40% RH, and the time required until the emission luminance is reduced to half of the initial emission luminance is measured. . The longer the time, the better the light emission life.
(Abrasion resistance)
The surface of the sealing layer was rubbed 3 times with a load of 0.5 kg using # 0000 steel wool, and then the peeled state of the sealing layer or the number of scratches on the surface was visually counted. The more the sealing layer does not peel and the fewer the number of scratches, the better the scratch resistance.

Example 4
FIG. 3 is a cross-sectional view of a light emitting device in Example 4 of the present invention.
On the glass substrate 16, ITO was formed to a thickness of 200 nm as the lower electrode layer 54 in a DC sputtering apparatus whose pressure was reduced to 10 ⁻² Pa or less. At this time, the deposition rate was 30 nm / min. Next, 8-hydroxyquinoline aluminum (hereinafter referred to as Alq3) was formed as a light emitting material layer 62 with a film thickness of 70 nm by a resistance heating vapor deposition apparatus reduced in pressure to 10 ⁻⁴ Pa or less. The vapor deposition rate at this time was 0.5 nm / min. Next, Al was formed with a film thickness of 100 nm as the upper electrode layer 55 in the same resistance heating vapor deposition apparatus.
Next, the transparent resin base material side of the laminate 100 obtained in Example 1 is placed on the glass substrate 16 and the epoxy adhesive 300 so as to cover the lower electrode 54 to the upper electrode 55 formed on the glass substrate 16. Thus, a light-emitting element 200 having the sealing layer 105 was obtained. Table 2 shows the evaluation results of the light-emitting element 200 obtained.

Example 5
FIG. 4 is a cross-sectional view of a light emitting device in Example 5 of the present invention.
On the laminated body 100 obtained in Example 1, ITO is 200 nm as the lower electrode layer 56, Alq3 is 70 nm as the light emitting material layer 63, and Al is 100 nm as the upper electrode layer 57, in the same manner as in Example 4. Were formed sequentially. Next, the laminate 100 and the glass lid 400 were bonded with an epoxy adhesive 301 so as to cover the lower electrode 56 to the upper electrode 57 formed on the laminate 100, whereby the light emitting element 201 was obtained. Table 2 shows the evaluation results of the light-emitting element 201 obtained.

Example 6
FIG. 5 is a cross-sectional view of a light emitting device in Example 6 of the present invention.
On the glass substrate 14, ITO was formed in a thickness of 200 nm as the lower electrode 50, Alq3 was 70 nm as the light emitting material layer 60, and Al was 100 nm as the upper electrode 51 in the same manner as in Example 4.
Next, the alicyclic structure-containing polymer is evaporated in an electron beam vapor deposition apparatus first decompressed to a vacuum of 10 ⁻² Pa or less so as to cover the lower electrode 50 to the upper electrode 51 on the glass substrate 14. An organic film 26 of 300 nm was formed by simultaneously evaporating SiO ₂ at a rate of 90 nm / min and an evaporation rate of 10 nm / min. Next, a 200 nm SiO ₂ inorganic film 38 was formed in a DC sputtering apparatus whose pressure was reduced to 10 ⁻² Pa or less. Further, in the same manner, the organic film 27 and the inorganic film 39 were sequentially stacked according to the material, and the light emitting element 202 having the sealing layer 44 was obtained. Table 2 shows the evaluation results of the light-emitting element 202 obtained.

Example 7
FIG. 6 is a cross-sectional view of a light emitting device in Example 7 of the present invention. On the laminate 100 obtained in Example 1, the ITO film as the lower electrode 58, the thickness of Alq3 as the light emitting material layer 64, 70 nm, and the upper electrode 59, Al as the film thickness of 100 nm, were sequentially formed in the same manner as in Example 4. Formed.
Next, the transparent resin substrate side of the laminate 100 obtained in Example 1 is bonded to the laminate 100 and the epoxy adhesive 302 so as to cover the lower electrode 58 to the upper electrode 59 on the laminate 100. Thus, a light-emitting element 203 having the sealing layer 105 was obtained. Table 2 shows the evaluation results of the light-emitting element 203 obtained.

Example 8
FIG. 7 is a cross-sectional view of a light emitting device in Example 8 of the present invention.
On the laminate 100 obtained in Example 1, the ITO film as the lower electrode 52, the thickness of the light emitting material layer 61, Alq3 as 70 nm, and the upper electrode 53 as Al, the film thickness of 100 nm, were sequentially formed in the same manner as in Example 4. Formed.
Next, a sealing layer 44 was formed by the same method as in Example 6 so as to cover from the lower electrode 52 to the upper electrode 53 on the multilayer body 100, whereby a light emitting element 204 was obtained. Table 2 shows the evaluation results of the light-emitting element 204 obtained.

Comparative Example 2
Example 6 except that the organic films 26 and 27 of Example 6 are organic films (SiO ₂ free) formed by forming an alicyclic structure-containing polymer with a film thickness of 300 nm by an electron beam at an evaporation rate of 90 nm / min. In the same manner as described above, a light emitting element was obtained. Table 2 shows the evaluation results of the obtained light-emitting element.

Comparative Example 3
The sealing layer 44 of Example 6 introduces tetrafluoroethylene into the vacuum chamber at an evaporation flow rate of 100 sccm (= 0.169 Pa · m ³ / s) without forming the inorganic films 38 and 39, and performs plasma CVD. A light emitting device was obtained in the same manner as in Example 6 except that a single layer of an organic film was formed by the method. At this time, the film formation rate was 90 nm / min and the film thickness was 300 nm. Table 2 shows the evaluation results of the obtained light-emitting element.

Comparative Example 4
The sealing layer 44 of Example 6 introduces hexamethyldisiloxane into the vacuum chamber at an evaporation flow rate of 100 sccm (= 0.169 Pa · m ³ / s) without forming the inorganic films 38 and 39, and plasma A light emitting device similar to that in Example 6 was obtained except that a single layer of an organic film was formed by CVD. At this time, the film formation rate was 90 nm / min and the film thickness was 300 nm. Table 2 shows the evaluation results of the obtained light-emitting element.

The following can be seen from the results in Table 2. As shown in the examples, an EL element using the laminate of the present invention for a transparent substrate or an EL element in which an organic layer, which is a feature of the present invention, is laminated on a sealing layer has light emission intensity, light emission lifetime, scratch resistance, Excellent adhesion and water vapor barrier properties.
On the other hand, as shown in the comparative example, an EL device in which the laminate of the present invention was not used as a transparent substrate and SiO ₂ was not included in the organic film of the sealing layer composed of a laminate of an inorganic film and an organic film (Comparative Example 2 ) Is inferior in light emission life, adhesion and water vapor barrier properties.

It is sectional drawing which shows the structure of a typical organic EL element. It is sectional drawing which shows an example of the laminated body of this invention. It is sectional drawing which shows an example of the light emitting element of this invention. It is sectional drawing which shows an example of the light emitting element of this invention. It is sectional drawing which shows an example of the light emitting element of this invention. It is sectional drawing which shows an example of the light emitting element of this invention. It is sectional drawing which shows an example of the light emitting element of this invention.

Explanation of symbols

  12: Transparent resin base material, 42: Sealing film, 33 and 34: Inorganic film, 23: Organic film

Claims (10)

A laminate comprising a sealing film formed by laminating at least one inorganic film and at least one organic film, and a transparent resin base material,
A laminate in which the organic film is a film made from at least a metal or metalloid simple substance or compound and an alicyclic structure-containing polymer. The light emitting element which is a laminated body according to claim 1, wherein a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked. The light emitting device according to claim 1, wherein a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially laminated, and the substrate is a laminate according to claim 1. A substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer and a sealing layer are sequentially laminated,
The sealing layer is a sealing film formed by laminating at least one inorganic film and at least one organic film;
A light-emitting element in which the organic film is a film using at least a metal or metalloid simple substance or compound and an alicyclic structure-containing polymer as raw materials. A substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer and a sealing layer are sequentially laminated,
The light emitting element whose said board | substrate and sealing layer are the laminated bodies of Claim 1. A substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer and a sealing layer are sequentially laminated,
The substrate is a laminate according to claim 1,
The sealing layer is a sealing film formed by laminating at least one inorganic film and at least one organic film;
A light-emitting element, wherein the organic film is a film using at least a metal or semimetal simple substance or compound and an alicyclic structure-containing hydrocarbon polymer as raw materials. The light emitting device according to any one of claims 2 to 6, wherein the light transmittance in the wavelength range of 400 nm to 800 nm is 80% or more when no light is emitted. A planar light source comprising the light emitting device according to claim 2. A dot matrix display device comprising the light emitting device according to claim 2. A liquid crystal display device comprising the light emitting device according to claim 2 as a backlight.

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