JP2002134271A - Sealed el element sealed by using barrier nature laminating structure object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealed EL element having a barrier nature laminating structure object, which has preferably transparency, crookedness, heat resistance, and weather-proof, not only preventing penetration of steam, oxygen, or the like, which are the degradation factors of the EL element, and controlling the degradation of the EL element. SOLUTION: The EL element consists of a 1st electrode, an EL layer formed on the 1st electrode, and a 2nd electrode formed on the EL layer, at least. The EL element is sealed using a barrier nature laminating structure object, which is constituted with two or more layer of barrier nature base material, which consist of a barrier cost layer and a barrier layer base, at least.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a sealed EL element for preventing deterioration of an EL element by sealing the EL element with a barrier layer for preventing oxygen and moisture from permeating.

[0002]

2. Description of the Related Art An EL element, particularly an organic thin film EL element using an organic substance as a light-emitting material, has a high luminous efficiency such as realizing high-luminance light emission even when an applied voltage is slightly less than 10 V, and has a simple element structure. It can emit light and is expected to be applied to displays and the like.

[0003] Such an EL element is deteriorated by water vapor or oxygen and the like, and its light emitting characteristics are deteriorated. Therefore, sealing with a layer having extremely low water vapor or oxygen permeability, that is, a barrier layer is often performed. However, depending on the usage of the EL element, this barrier layer is subject to deterioration, deformation, and destruction,
Barrier performance may be reduced. And especially E
The driving of the L element is accompanied by heat generation, and it can be expected that the element is left in a sunshine irradiation and a high-temperature atmosphere under a specific environment such as in an automobile. Therefore, a demand for imparting weather resistance and heat resistance to the barrier layer is required. Is growing. Also, EL
In applications where the device requires transparency and flexibility, sealing with a barrier layer having flexibility is required. However, in the existing barrier layer having flexibility, a sufficient barrier effect cannot be obtained because the barrier performance is low and water vapor and oxygen permeate.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an EL having a flexible barrier layer which solves the above-mentioned problems.
Providing an element, that is, an EL element having a flexible barrier layer in which permeation of water vapor, oxygen, or the like, which is a deterioration factor of the EL element, is prevented, and preferably has transparency, heat resistance, and weather resistance. To provide an EL element having

[0005]

Means for Solving the Problems The present inventor has developed a barrier laminate structure by laminating a plurality of specific barrier substrates for blocking oxygen and moisture (the barrier laminate structure has flexibility). It has been found that the above problem can be solved by forming a barrier layer), and the present invention has been completed.

Accordingly, an EL element according to the present invention is an EL element comprising at least a first electrode, an EL layer formed on the first electrode, and a second electrode formed on the EL layer, The EL device is characterized in that the EL device is sealed using a barrier laminate structure in which at least two barrier substrates each composed of a barrier coat layer and a barrier layer base are laminated.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Encapsulation having barrier laminate structure
Structure Figure 1 EL element, sealing EL having barrier laminate structure of the present invention
It is sectional drawing of an example of an element, FIG. 2 is the top view.
In the sealed EL device having the barrier laminate structure shown in these figures, a second barrier layer 2 (generally called a protective layer) is provided on a first barrier layer 1 (generally called a base).
Are bonded by a sealing layer 3, and the first electrode 4 is provided in a space surrounded by the first barrier layer, the second barrier layer and the sealing layer.
An EL element including at least an EL layer 5 formed on the first electrode and a second electrode 6 formed on the EL layer is arranged. Note that, in the peripheral portion of the first barrier layer,
Preferably, an extraction electrode can be provided.

[0008] In the barrier layer herein, a layer generally with barrier property is referred to as a barrier layer, barrier laminate structure what flexibility obtained by laminating a specific barrier substrate to be described later of the barrier layer Call. In this specification, in the case where the EL element is sealed by sandwiching it between two barrier layers, a material that also functions as a support layer of the EL element may be replaced with a material that does not function as a first barrier layer or a base material or a support layer. It may be called a second barrier layer or a protective layer.
Among them, for the substrate, for example, a glass substrate or a film substrate having a barrier property can be used, and for the protective layer, for example, a glass having a barrier property, a film, a material obtained by laminating a film on glass, and laminating films are used. It can be a combination of things.

In the present specification, having a barrier property means
The permeability of water and oxygen is extremely low. Specifically, the permeability of water is 1 × 10 ⁻³ (gram · m ² / da).
y · atm) or less, oxygen permeability is 1 × 10 ⁻² (gr)
am · m ² / day · atm).

[0010] The barrier layer having heat resistance preferably has a glass transition temperature or a melting temperature of 100 ° C., for example, to the extent that it can withstand the temperature at the time of mounting driving.
The above refers to the barrier layer. The barrier layer having weather resistance is not limited as long as it can withstand the mounting operation, but is preferably, for example, JIS C8917: 19.
98 that satisfy the criteria of weather resistance described in Annex 5 (normative) Light irradiation test A-5.

(Barrier Substrate) The barrier substrate in the present specification is a layer having relatively low permeability to water and oxygen, although not as low as the barrier layer described above. Permeability is 1 × 10 ⁻¹ (gram · m ² / day · atm)
Hereinafter, the oxygen permeability is 1 × 10 ⁻¹ (gram · m ² /
day · atm) or less, for example, a thickness of 5
It is available as a film having a thickness of 0 to 1000 μm.

The barrier substrate comprises at least a barrier coat layer and a barrier layer base. Examples of such a barrier substrate include silica-deposited PET (polyethylene terephthalate) manufactured by a chemical vapor deposition method,
Silica-deposited PET manufactured by a physical vapor deposition method.

Examples of the barrier coat layer constituting the barrier substrate include, for example, a layer formed by depositing a fluorine-based compound by a chemical vapor deposition method in addition to an inorganic oxide film such as the above-mentioned silica vapor-deposited layer. . The thickness of the barrier coat layer is preferably from 50 to 5000 °, more preferably from 500 to 1000 °, because a thick film causes film defects such as cracks due to slight bending.

The inorganic oxide film typically includes a thin film obtained by depositing a metal oxide. For example, silicon (Si), aluminum (Al), magnesium (M
g), calcium (Ca), potassium (K), tin (S
n), sodium (Na), boron (B), titanium (T
A vapor-deposited thin film of an oxide of a metal such as i), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. Preferable examples include vapor-deposited thin films of oxides of metals such as silicon (Si) and aluminum (Al). Such an oxide is MOx (provided that
In the formula, M represents a metal element, and the value of X varies depending on the metal element. ), And X
Of silicon (Si) are 0 to 2, aluminum (Al) is 0 to 1.5, and magnesium (M
g) is 0-1, calcium (Ca) is 0-1, potassium (K) is 0-0.5, tin (Sn) is 0-2,
Sodium (Na) is 0-0.5, and boron (B) is
0, 1, 5, titanium (Ti): 0, 2, lead (Pb)
Can take a value in the range of 0 to 1, zirconium (Zr) takes a value of 0 to 2, and yttrium (Y) takes a value of 0 to 1.5. When X = 0, it is not suitable for use because it is completely metal and not transparent. Further, the upper limit of the range of X is a value that is completely oxidized. Preferably, M is silicon or aluminum and for silicon (Si) X
However, X is 1.0 to 2.0, and in aluminum (Al),
Those having a value in the range of 0.5 to 1.5 can be used. In the present invention, the thickness of the inorganic oxide thin film as described above varies depending on the type of the metal or the metal oxide used, for example, about 50 to 2000 °,
Preferably, it is desirably formed by arbitrarily selecting in the range of about 100 to 1000 °. In the present invention, the inorganic oxide vapor-deposited thin film is not limited to one layer of the inorganic oxide vapor-deposited thin film, but may be a laminate of two or more layers. Alternatively, as the metal oxide, one kind or a mixture of two or more kinds can be used to form a thin film of an inorganic oxide mixed with different materials.

A barrier coat layer may be formed by laminating a resin material for significantly improving the barrier property on the inorganic oxide film. Examples of such a resin material include a layer made of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle. In forming a layer composed of a resin composition containing an ethylene-vinyl alcohol copolymer as a main component of a vehicle, for example, as a material,
One or more ethylene-vinyl alcohol copolymers are the main component of the vehicle, and if necessary, furthermore, light stabilization, for example, of fillers, stabilizers, plasticizers, antioxidants, ultraviolet absorbers and the like. Agents, dispersants, thickeners, desiccants, lubricants, antistatic agents, cross-linking agents, optional additives such as solvents, solvents, diluents and the like, which are sufficiently kneaded with a solvent type, an aqueous type, Alternatively, a resin composition of an emulsion type or the like can be used. Then, using this resin composition, for example, a roll coating method, a gravure roll coating method, a kiss roll coating method, a squeeze roll coating method,
Coating amount, for example, about 0.1 to 10 g / m ² , preferably 0.5 g by coating such as reverse roll coating method, curtain flow coating method and the like.
５5 g / m ² (in a dry state), followed by drying by heating and further aging treatment. As the resin composition, an ethylene-vinyl alcohol copolymer or the like is dissolved or kneaded, and since these are further cured,
It is preferable to use a resin composition prepared using an alcohol-water-based solution or the like. Examples of the alcohol component include n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, ethyl alcohol, and methyl alcohol. Etc. can be used
In the above-mentioned alcohol-water solution, it is desirable to prepare an alcohol-water solution by mixing the alcohol and water in a proportion of, for example, 50 to 30 parts by weight of water to 50 to 70 parts by weight of alcohol. As the ethylene-vinyl alcohol copolymer, for example, an ethylene-vinyl acetate copolymer in which the content of vinyl acetate is about 79 to 92% by weight is completely saponified, the ethylene content of which is 2
5 to 50 mol% of ethylene-vinyl alcohol copolymer can be used. Ethylene-vinyl alcohol copolymer has high gas bath properties, and is also excellent in fragrance retention, transparency, and the like. When the ethylene content is 50 mol% or more, the oxygen gas barrier property sharply decreases,
In addition, the transparency is deteriorated, and when the content is 25 mol% or less, the thin film becomes brittle, and the oxygen gas barrier property is reduced under high humidity. The above coating film is
Excellent in tight adhesion with the inorganic oxide thin film, the adhesive strength between the two is extremely strong, no phenomenon such as peeling between the layers is observed, and in the present invention, the inorganic oxide thin film and the coating layer A barrier layer composed of two layers is formed, thereby further improving the barrier properties against oxygen gas, water vapor gas, etc., and also excellent in transparency, heat resistance, hot water resistance, lamination suitability, etc. A laminated structure can be manufactured.

Further, as the material constituting the barrier layer base of the barrier substrate, a material having heat resistance and weather resistance is more preferable. Specific examples of preferred materials include, for example, cyclic polyolefin-based resins, polystyrene-based resins,
Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer, (A
BS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin,
Polyester resins such as polyethylene terephthalate (PET) or polyethylene terephthalate, polyamide resins such as various nylons, polyimide resins, polyamide imide resins, polyaryl phthalate resins,
Silicone-based resins, polysulfone-based resins, polyphenylene sulfide-based resins, polyethersulfone-based resins, polyurethane-based resins, acetal-based resins, cellulose-based resins, and copolymers obtained by copolymerizing the above-listed precursors, The mixed resins listed above are exemplified. More preferable materials include, for example, polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA) composed of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, and copolymer of tetrafluoroethylene and hexafluoropropylene (FEP). ), Copolymers of tetrafluoroethylene and perfluoroalkylvinyl ether and hexafluoropropylene (EPE), copolymers of tetrafluoroethylene and ethylene or propylene (ETFE), polychlorotrifluoroethylene resin (PCTFE), ethylene and chlorotri Fluoroethylene copolymer (ECTF
E), a fluorine-based resin composed of one or more fluorine-based resins such as vinylidene fluoride-based resin (PVDF) or vinyl fluoride-based resin (PVF).

If the thickness of the barrier layer base is too large, the difference in expansion and contraction between the inner wall and the outer wall with respect to bending becomes large, and the light transmittance is reduced.
More preferably, it can be 50 to 100 μm.

(Barrier laminated structure) Sealed EL of the present invention
In the device, the barrier laminate structure forms at least a part of a barrier layer that seals the EL device. Specifically, for example, both sides or one side when sealing by sandwiching between two sheet-like barrier layers can be constituted by a barrier laminate structure.

The barrier laminate structure of the present invention is obtained by laminating the above-mentioned barrier base material, and has a sufficient barrier property similar to that of the barrier layer. The number of layers of the barrier substrate is not limited as long as it is 2 or more, but preferably 2 to 5, and more preferably 2 to 3, the barrier performance is maintained while maintaining sufficient flexibility and transparency. It is preferable because it can be increased. In addition, it is preferable that the barrier laminate has a structure in which two or more types of barrier substrates having different oxygen permeability or water permeability are laminated, since the barrier property is further enhanced. Furthermore, the thickness of the barrier laminate structure after lamination is preferably 50 to 3000 μm. By superposing two or more sheets in this way, an unexpected performance improvement effect can be obtained even if the performance is hardly improved even if the thickness of the barrier layer is simply increased.

The method of laminating between the barrier base materials and the method of forming the adhesive layer are not particularly limited, and examples thereof include a dry lamination method, an extrusion coating method, an ultrasonic fusion method, a lamination method, a die coating method, gravure printing, and offset printing. Printing methods.

In laminating the barrier substrates, the barrier substrates can be adhered or simply adhered, or a space can be provided between the barrier substrates. Preferably, a space is provided between the barrier base materials and an inert substance is sealed in the space, since the barrier performance can be improved while maintaining sufficient flexibility and transparency. Examples of such an inert substance include a liquid selected from silicon oil and a silane coupling agent, and a gas selected from nitrogen, argon, and the like.

Preferably, water is trapped between the barrier substrates.
An adhesive layer that can enclose the agent or contains a water catching agent
Can be provided. As a water catching agent, chemically
Adsorbs water and maintains a solid state even if it absorbs moisture
Any of them can be used. Such a substance
For example, alkali metals, alkaline earth metals,
Li metal oxide, alkaline earth metal oxide, sulfate, metal
Halides, perchlorates and organic substances. Catching water
Among the agents, alkali metals and alkaline earth metals include L
i, Na, K, Rb, Cs, Fr, Be, Mg, Ca,
Sr, Ba, Ra and the like can be mentioned. Also, among the water absorbing agents
As the alkali metal oxide, sodium oxide (Na₂
O), potassium oxide (K₂O);
As the earth metal oxide, calcium oxide (Ca
O), barium oxide (BaO), magnesium oxide (M
gO). Among the water-absorbing agents, sulfates
Lithium oxide (Li₂SO₄), Sodium sulfate (Na₂
SO₄), Calcium sulfate (CaSO₄), Magnesium sulfate
Cium (MgSO₄), Cobalt sulfate (CoSO₄),
Gallium sulfate (Ga₂(SO₄)₃), Titanium sulfate (T
i (SO₄)₂), Nickel sulfate (NiSO₄)etc
No. These sulfates are preferably used as anhydrous salts.
You. Among the water trapping agents, metal halides include
Cium (CaCl ₂), Magnesium chloride (MgC
l₂), Strontium chloride (SrCl₂), Chloride
Thorium (YCl₃), Copper chloride (CuCl₂), Fluoridation
Cesium (CsF), tantalum fluoride (TaF₅),
Niobium nitride (NbF₅), Calcium bromide (CaB)
r₂), Cerium bromide (CeBr)₃), Selenium bromide (S
eBr₄), Vanadium bromide (VBr₂) 、 Magnesium bromide
Cium (MgBr₂), Barium iodide (BaI₂),
Magnesium iodide (MgI₂). This
As these metal halides, anhydrous salts are preferably used.
In addition, perchlorate is a perchlorate
Um (Ba (ClO₄)₂), Magnesium perchlorate
(Mg (ClO₄)₂). These perchlorines
As the salt, an anhydrous salt is preferably used.

Examples of the material that can be used for the adhesive layer of the barrier substrate include a photo-curable resin and a thermosetting resin. Preferably, a low moisture permeable adhesive having a water vapor barrier property of 30 g / (m ² · day · atom) or less is used. Specifically, for example, an acrylic resin or an epoxy resin, for example, a resin obtained by adding 1% of PF120 as a spacer to XNR5515 manufactured by Nagase Ciba Co., Ltd. is used. When the lamination is performed by a dry lamination method, the adhesive is, for example, ethyl acetate as a diluting solvent, a polyester polyol as a main component, and a required amount of an isocyanate-based material as a curing agent, a urethane-based adhesive. Can be used. In the case of laminating by a molten resin extrusion coating method, for example, low density polyethylene can be used.

Hereinafter, as a preferred specific example of the above-mentioned method for producing a barrier laminate structure, a barrier substrate made of silica-deposited PET is laminated by a molten resin extrusion coating method to produce a barrier laminate structure. The method for forming the barrier laminate structure used in the sealed EL device of the present invention is not limited to this method.

The lamination of the barrier substrate (deposited PET) is preferably carried out, for example, by coating an adhesive on the outermost layer (first layer) of PET and drying it in a drying hood, and then depositing the second layer of deposited PE.
It can be bonded by laminating with the vapor deposition film side of T and then winding it up on a winding roll. Furthermore,
Deposition P of a rolled-up barrier laminate having a single layer of PET of the outermost layer (first layer) and PET of the second layer
The ET side is coated with an adhesive, dried with a drying hood, and then laminated with the third layer of the deposited PET film and rolled up, whereby multilayer lamination of the barrier substrate can be performed. Here, the coating of the adhesive is preferably 2 to 5 g in terms of solid content using a coating method such as gravure coding.
/ M ² of adhesive can be coated.
When coating the adhesive by the molten resin extrusion coating method, preferably, for example, a molten low-density polyethylene is extruded with a T die, and the extruded film is preferably 20 to
It can be performed by extruding about 100 μm.

Preferably, a primer layer can be provided on the deposition surface of the deposited PET. This primer layer is preferably prepared by adding an epoxy silane coupling agent (8.0% by weight) and an antiblocking agent (1.0% by weight) to, for example, an initial condensate of a two-component curable polyurethane resin. And sufficiently kneaded to prepare a primer resin composition, which is then coated with a gravure roll coat method to a film thickness of 0,0.
It can be formed by coating to 5 g / m ² (dry state). Preferably, an anchor coat agent layer can be provided on the surface of the primer layer. This anchor coating agent layer is preferably formed by coating, for example, a two-component curable urethane-based anchor coating agent to a thickness of 0.1 g / m ² (dry state) by a gravure roll coating method. it can.

According to such a method, the barrier base material is
When the laminated barrier laminate structure (PET / EC / (deposition surface) vapor-deposited PET / EC / (deposition surface) vapor-deposited PET) is manufactured, a water vapor barrier: 0.01 g · m ² · day (temperature 40 ° C. humidity 90) % Measurement), oxygen barrier: 0.2cc
/ M ² · day (measured at a temperature of 23 ° C. and a humidity of 0%).

The configuration of the barrier laminate structure is not particularly limited as long as a plurality of barrier substrates are laminated as described above, and specific configurations include, for example, the following. Note that DL is an abbreviation for dry lamination, and EC is an abbreviation for molten resin extrusion coating. PET / DL / (deposited surface) Deposited PET / DL / (deposited surface) Deposited PET PET / DL / (deposited surface) Deposited PET / DL / (deposited surface) Deposited PET / DL / (deposited surface) Deposited PET PET / DL / (Evaporated surface) evaporated PET / DL / (evaporated surface) evaporated PET / DL / (evaporated surface) evaporated PET / DL /
(Evaporation surface) Evaporation PET PET / DL / (Evaporation surface) Evaporation PET / DL / (Evaporation surface) Evaporation PET / DL / (Evaporation surface) Evaporation PET / DL /
(Evaporation surface) Evaporation PET / DL / (Evaporation surface) Evaporation PET PET / EC / (Evaporation surface) Evaporation PET / EC / (Evaporation surface) Evaporation PET PET / EC / (Evaporation surface) Evaporation PET / EC / (Evaporation surface ) Evaporated PET / EC / (Evaporated surface) Evaporated PET PET / EC / (Evaporated surface) Evaporated PET / EC / (Evaporated surface) Evaporated PET / EC / (Evaporated surface) Evaporated PET / EC /
(Evaporation surface) Evaporation PET PET / EC / (Evaporation surface) Evaporation PET / EC / (Evaporation surface) Evaporation PET / EC / (Evaporation surface) Evaporation PET / EC /
(Evaporation surface) Evaporated PET / EC / (Evaporation surface) Evaporated PET Arrangement in which the above is arbitrarily overlapped or bonded

This barrier laminated structure preferably has an average light transmittance of 80% or more in the visible light region. Such a barrier laminate structure having a high transmittance is advantageous when light is extracted from the EL element from the barrier laminate structure side. This transmittance is, for example, a transmittance at which at least two barrier layer bases can be stacked even if the transmittance of one barrier layer base is 90%.

The sealing of the EL element with the barrier layer is performed using a material that does not allow water or oxygen to enter the sealing portion, that is, a material that does not impair the barrier performance of the barrier layer. 30
(gram · m ² / day · atm) or less can be used. Such a sealing material is not limited as long as it is a substance having low permeability to water and oxygen. As such a sealing material, specifically, for example, XNR5 manufactured by Chise Nagase Co., Ltd.
515 is a resin in which 1% of PF120 is added as a spacer, and the thickness of an adhesive portion passing from the outside of the barrier layer to the inside of the barrier layer is 1 mm or more. Also,
Normally the material is carried out under a dry N ₂ atmosphere.

As the material for sealing the EL element by bonding between the barrier laminate structures or between the substrate and the protective layer, for example, a photo-curable resin or a thermosetting resin used for laminating the barrier substrate is used. Can be mentioned.

EL Element In the present invention, the EL element sealed by the barrier layer is not particularly limited, and includes a first electrode, an EL layer formed on the first electrode, and a first electrode formed on the EL layer. Any EL element having at least two electrodes may be used. The features of the present invention can be more advantageously used in a flexible EL element, a transparent EL element, and an organic EL element in which deterioration due to water or oxygen is particularly problematic.

[0033]

EXAMPLES The following coating solutions were prepared. Coating liquid 1 (for forming a hole injection layer) An aqueous dispersion of poly 3,4-ethylenedioxythiophene / polystyrene sulfonate (abbreviated as PEDOT / PSS, trade name Baytron PTP AI 4083, Bayer) was used as coating liquid 1.

Coating Liquid 2 (for forming EL layer) A coating liquid 2 was prepared by dissolving 1 part by weight of a polyfluorene derivative in 66.7 parts by weight of xylene.

The polyfluorene derivative used for the coating solution 2 was synthesized by the following method. Under a dry nitrogen stream, 5.0 g (30 mmol) of fluorene was dissolved in dry tetrahydrofuran, 22 ml (35 mmol) of a 1.6 M normal butyllithium hexane solution was added dropwise at -78 ° C, and the mixture was stirred at -78 ° C for 1 hour. Subsequently, 4.9 ml (35 mmol) of normal hexyl bromide was added dropwise thereto, and the mixture was stirred at -78 ° C for 1 hour and further at room temperature for 1 hour.
Subsequently, similarly, 22 ml (35 mmol) of 1.6 M normal butyllithium hexane solution was added dropwise at -78 ° C, and the mixture was stirred at -78 ° C for 1 hour. Subsequently, 4.9 ml (35 mmol) of normal hexyl bromide was added dropwise thereto, and the mixture was stirred at -78 ° C for 1 hour and further at room temperature for 1 hour.
After water was added dropwise under ice-cooling, the mixture was extracted with ethyl acetate, dehydrated and dried over magnesium sulfate, and the solvent was distilled off. This was recrystallized from hexane to obtain 9.5 g (95%) of 9,9-dihexylfluorene.

2,9-dihexylfluorene 2.0 g
(6.0 mmol), 0.02 g of iron (III) chloride (0.
12 mmol) was dissolved in 9 ml of chloroform, and 1.2 g of bromine dissolved in 3 ml of chloroform was added dropwise to a solution stirred at 0 ° C. under light shielding. The mixture was stirred at room temperature for 18 hours, washed with an aqueous solution of sodium thiosulfate, dried over magnesium sulfate and dried, and the solvent was distilled off. The residue was separated and purified by column chromatography (eluent: hexane) to obtain 2.4 g (92%) of 2,7-dibromo-9,9-dihexylfluorene.

Under a stream of dry nitrogen, 2,7-dibromo-9,
2.0 g (4.0 mmol) of 9-dihexylfluorene
Was dissolved in 40 ml of dry tetrahydrofuran, 5.3 ml (8.4 mmol) of 1.6 M normal butyl lithium hexane solution was added dropwise thereto under ice cooling, and the mixture was stirred at 0 ° C for 1 hour. Subsequently, 2-isopropoxy-4,4,4
2.0 ml (10 mmol) of 5,5-tetramethyl-1,3,2-dioxaborane was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour and further at room temperature for 12 hours. After water was added dropwise under ice-cooling, the mixture was extracted with diethyl ether, dried over magnesium sulfate and dried, and the solvent was distilled off. The residue was washed with ethanol and recrystallized with a mixed solution of ethanol / hexane to give 2,7-bis (4,4,5,5-tetramethyl-
1.4 g (60%) of (1,3,2-dioxaboran-2-yl) -9,9-dihexylfluorene were obtained.

Under a dry nitrogen stream, 2,7-bis (4,4,4
5,5-tetramethyl-1,3,2-dioxaborane-
2-yl) -9,9-dihexylfluorene 0.53 g
And 0.45 g of 2,7-dibromo-9,9-dihexylfluorene and 0.02 g of tetrakis (trisphenylphosphine) palladium were dissolved in 18 ml of dry toluene, and 27 ml of a 2M aqueous sodium carbonate solution was added thereto. For 48 hours. After cooling, the mixture was poured into methanol, and the solid content was washed with a dilute aqueous hydrochloric acid solution. Then, using acetone as a solvent, dissolved components were removed with a Soxhlet refluxer to separate insoluble portions. This was dissolved in chloroform and reprecipitated with methanol to obtain the desired polyfluorene derivative.

Fabrication of sealing barrier laminate structures 1, 2, and 3
The following laminated barrier barrier structure for sealing was produced. PET / DL / (deposited surface) deposited PET / DL equivalent to the above
/ (Evaporation surface) Evaporated PET (DL is dry lamination) was used as the barrier laminate structure 1. The PET / DL / (deposition surface) vaporized PET / DL / (deposition surface) vaporized PET / DL / (deposition surface) vaporized PET corresponding to the above was used as the barrier laminate structure 2. PET equivalent to the above
The barrier laminate structure 3 was formed of / DL / (deposited surface) deposited PET / DL / (deposited surface) deposited PET / DL / (deposited surface) deposited PET / DL / (deposited surface) deposited PET.

At the center of the EL device, an ITO glass substrate patterned into a strip having a width of 12 mm was subjected to cleaning and surface treatment, and a coating solution 1 was applied thereon by a spin coater. This is heated and dried in a clean oven at 200 ° C. for 5 minutes to obtain a film thickness of 1
A thin film of 00 nm was formed. Subsequently, the coating liquid 2 was applied by a spin coater to form a 100 nm thin film.
Finally, as an upper electrode, 0.5 nm of LiF and 150 nm of aluminum were vapor-deposited by mask so as to be orthogonal to the pattern of ITO. Green light emission was obtained by driving the ITO electrode and the upper Al electrode as address electrodes.

Sealed EL device having barrier laminate structure
The produced EL element was sealed. The sealing is performed in a dry nitrogen atmosphere, and the barrier laminate structure 1 and the barrier laminate structure 2
And UV curable resin (trade name XNR551 manufactured by Nagase Chiba Co., Ltd.)
5 with 1% of PF120 added as a spacer)
Was performed.

Evaluation of Degradation When these EL devices were left in the air for a certain period of time, the light emission characteristics of the devices were measured by applying a voltage to the EL devices. The light emission characteristics were evaluated by measuring a current value flowing through the EL element having a correlation with the luminance of the EL element.

FIG. 3 is a graph showing the change over time of the relative current value when the current value on the production day is I0 in this embodiment. Compared to the barrier laminate structure 1 having the two-layer barrier substrate structure, the barrier laminate structure 2 having the three-layer barrier substrate structure is:
Further, it can be seen that the barrier laminated structure 3 having the four-layered barrier substrate has little deterioration of the EL element.

[0044]

According to the present invention, it is possible not only to prevent the permeation of water vapor, oxygen and the like, which are the causes of deterioration of the EL element, but also to suppress the deterioration of the EL element, and it is also preferable to improve the transparency, flexibility, heat resistance and weather resistance. E having barrier laminate structure having
An L element can be provided.

[Brief description of the drawings]

FIG. 1 shows a sealing EL having a barrier laminate structure of the present invention.
It is sectional drawing of an example of an element.

FIG. 2 shows a sealing EL having a barrier laminate structure of the present invention.
It is a top view of an example of an element.

FIG. 3 is a graph showing a temporal change of a current value in the present embodiment.

[Description of Signs] 1 First barrier layer 2 Second barrier layer 3 Sealing layer 4 First electrode 5 EL layer 6 Second electrode

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3K007 AB11 AB13 AB18 BA06 BA07 BB01 BB03 BB04 BB05 CA01 CA05 CA06 CB01 DA01 DB03 EB00 FA02

Claims (16)

[Claims] 1. An EL element comprising at least a first electrode, an EL layer formed on the first electrode, and a second electrode formed on the EL layer, wherein the EL element is a barrier coat. A sealed EL element, characterized by being sealed using a barrier laminated structure obtained by laminating two or more barrier substrates each composed of a layer and a barrier layer base. 2. The method according to claim 1, wherein the barrier coat layer is formed by physical vapor deposition,
2. The sealed EL device according to claim 1, wherein the device is formed using a chemical vapor deposition method. 3. The sealed EL device according to claim 2, wherein said barrier coat layer is a layer made of an inorganic oxide. 4. The sealed EL device according to claim 1, wherein the barrier laminate has an average light transmittance of 80% or more in a visible light region. 5. The sealed EL device according to claim 1, wherein the barrier layer base has heat resistance and weather resistance. 6. The encapsulation E according to claim 1, wherein the barrier laminate structure is formed by laminating barrier substrates with each other by a dry lamination method or an extrusion coating method.
L element. 7. The sealing EL device according to claim 1, wherein the barrier laminate structure is formed by laminating barrier substrates with each other by using a photocurable resin or a thermosetting resin. 8. The sealed EL device according to claim 1, wherein the barrier laminate structure is formed by laminating barrier substrates with a low moisture-permeable adhesive layer. 9. The sealed EL device according to claim 1, wherein an inert substance is sealed between the barrier base materials of the barrier laminate structure. 10. The barrier coat layer has a thickness of 50 to 50.
The sealed EL device according to claim 1, wherein the angle is 00 °. 11. The barrier layer base has a thickness of 1 to 500.
The sealed EL device according to claim 1, wherein the thickness is μm. 12. The sealed EL device according to claim 1, wherein a water catching agent is sealed between the barrier base materials of the barrier laminate structure. 13. The sealed EL device according to claim 1, wherein an adhesive layer containing a water catching agent is provided between the barrier substrates of the barrier laminate structure. 14. The barrier base is made of a cyclic polyolefin resin, a polystyrene resin, acrylonitrile resin.
Styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer, (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate (PET) ), Polyester resins such as polyethylene terephthalate, polyamide resins, polyimide resins, polyamide imide resins, polyaryl phthalate resins, silicone resins, polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins, polyurethane resins The sealing EL element according to claim 1, comprising a material selected from a resin, an acetal resin, a cellulose resin, a copolymer thereof, and a mixed resin thereof. 15. The sealed EL device according to claim 1, wherein the barrier laminate structure is formed by laminating two or more types of barrier substrates having different oxygen permeability or water permeability. 16. The sealed EL device according to claim 1, wherein said EL device is an organic EL device.