JP2002141167A - Organic electroluminescent element and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element capable of preventing the generation of dark spots and retaining superior light emitting characteristics for a long period by a simple constitution. SOLUTION: This organic electroluminescent element is provided with an insulating substrate, a positive electrode formed on the insulating substrate, a light emitting part having an organic light emitting layer and a negative electrode, and an outside air shielding plate covering the light emitting part. A resin layer is formed in a clearance between the insulting substrate and the outside air shielding plate surrounding the light emitting part so as to seal the light emitting part. The resin layer is formed, on its outside surface, with a gas barrier film composed of a coating component including, (a) an ethylene- vinyl alcohol copolymer and at least one kind selected from among the group of (b) a metal alcoholate represented by R1mM(OR2)n, a hydrolysate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrorate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolysate of the metal acylate, and a condensate of the metal acylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic electroluminescent device and a method of manufacturing the same, and more particularly, to an organic electroluminescent device having excellent durability and a method of sealing the same.

[0002]

2. Description of the Related Art Thin-film electroluminescent (EL) elements conventionally used include rare earth elements (Eu), which are emission centers, in addition to inorganic materials such as CaS, ZnS, and SrS which are II-VI compound semiconductors. , Ce, Tb, Sm, etc.) and Mn-doped inorganic materials. However, when an inorganic material is used as the phosphor, there are problems that a high voltage is required and practical emission luminance cannot be obtained except for green and orange colors. In recent years, an EL element using an organic thin film containing a dye as a fluorescent substance has been developed instead of an EL element manufactured from such an inorganic material.

An organic EL device is an injection type EL in which electrons and holes are injected from an electrode into an organic phosphor (light-emitting layer). The organic phosphor is generated when the injected electrons and holes recombine. Excited state with the energy to emit light. Organic E
As the phosphor of the L element, an organic compound having a π-electron conjugated aromatic ring which emits fluorescence by light excitation is used. In the case of an organic EL device, light emission is two of fluorescence and phosphorescence.
The former is 25% of the luminescent component, and the latter is 75% of the luminescent component. However, phosphorescence is often shifted to the infrared side and does not contribute to visible light emission, so that the luminous efficiency is usually 25% or less. In order to increase the luminous efficiency, the type of the electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and a hole transport layer composed of an aromatic diamine and a luminescent layer composed of an aluminum complex of 8-hydroxyquinoline are used. Provided organic EL elements have been developed. According to this organic EL device, the luminous efficiency is greatly improved as compared with a conventional EL device using a single crystal such as anthracene or the like, and practical characteristics are approached.

In addition to the above EL devices using low molecular materials, poly (p-phenylenevinylene), poly (3-alkylthiophene), poly [2-methoxy-5- (2-ethylhexyloxy)-
Also, an EL device using a polymer material such as [1,4-phenylenevinylene] has been developed, and a device in which a polymer such as polyvinylcarbazole is mixed with a low-molecular light-emitting material and an electron transfer material has been developed.

In such an organic EL device, a transparent electrode such as indium tin oxide (ITO) is usually used as an anode, and magnesium, aluminum, calcium, or the like is used as a cathode in order to efficiently perform electron injection. A metal electrode having a low work function such as a silver alloy or a lithium alloy is used. However, these cathode materials are easily oxidized by moisture or oxygen in the air, and as a result, the cathode is separated from the organic layer, and a defect generally called a dark spot (a portion that does not emit light on the light emitting surface of the element) occurs. The number and size of dark spots in the organic EL device increase when the device is stored or driven for a long period of time. For this reason, the shortcoming of durability, which is the biggest problem of the organic EL element, is brought about. If the deterioration due to the dark spot of the organic EL element is not improved and the light emission characteristics are unstable, it is a serious problem for a light source such as a facsimile, a copying machine, a backlight of a liquid crystal display, and a display element such as a flat panel display. Is also undesirable. As described above, in order to improve the stability and reliability of the organic EL element, sealing for protecting the element from moisture and oxygen in the air is indispensable.

As a method of sealing an organic EL element, a method of inserting P ₂ O ₅ into an airtight case to block it from the outside air,
A method of molding with acrylic resin, a method of forming a protective film such as a metal oxide and then sealing it using a glass plate, a method of holding in an inert liquid made of fluorinated carbon, a plasma polymerized film on the element And a method of providing a photocurable resin layer, a method of providing a polymer protective film and then holding it in silicone oil, a method of encapsulating in liquid paraffin or silicone oil, and a method of coating polyvinyl alcohol on a protective film such as an inorganic oxide. A method of bonding an applied glass plate with an epoxy resin, using a moisture-resistant photocurable resin layer to
A method has been proposed in which a substrate having low water permeability is bonded onto an element via an O ₂ layer. However, none of the conventional methods for sealing an organic EL element is satisfactory. For example, a method of directly bonding and sealing an element with an ultraviolet-curing resin involves damage to the element by a solvent contained in the adhesive or damage by ultraviolet rays, and the stress is dissipated during curing, so that the cathode is peeled off from the organic layer and the like. Not a target.

Recently, an external air shielding plate is provided to cover the light emitting portion formed on the substrate, and a resin layer is formed in the gap between the substrate and the external shielding plate so as to surround the light emitting portion, thereby sealing the light emitting portion. In addition, there has been proposed an organic EL device in which a gas barrier film containing silicon oxide, nitride and / or oxynitride as a main component is formed on the outer surface of a resin layer (JP-A-11-144864). . Although this technique is effective as a method for sealing an organic EL element, it must be carried out under a high vacuum to form this gas barrier film, resulting in operability problems such as complicated processes. There is.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device having excellent durability by a simple means and a method for producing the same.

[0009]

The present invention comprises an insulating substrate, a light emitting portion having an anode, an organic light emitting layer, and a cathode formed on the insulating substrate, and an outside air shielding plate for covering the light emitting portion. In addition, a resin layer is formed so as to surround the light emitting portion in a gap between the insulating substrate and the outside air shielding plate to seal the light emitting portion, and the following components (a) and (b) are formed on the outer surface of the resin layer. The present invention relates to an organic electroluminescent device formed by forming a gas barrier film made of a coating composition containing a component. (A) Ethylene / vinyl alcohol copolymer (b) General formula (1) R ¹ _mm M (OR ² ) _n ··· (1) (wherein, M is a metal atom, and R ¹ is the same or different. , An organic group having 1 to 8 carbon atoms, R ² is the same or different,
An alkyl group of from 5 to 5 or an acyl group or phenyl group of from 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M) Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate At least one selected from the group consisting of a decomposition product and a condensate of the metal acylate, wherein the coating composition used in the organic electroluminescent device of the present invention includes:
Further, those containing a nitrogen-containing organic solvent are preferred. Further, the coating composition used in the organic electroluminescent device of the present invention preferably further contains (c) inorganic fine particles. Further, the gas barrier film may be a film in which a coating film formed from the coating composition is laminated on a synthetic resin film. Further, the gas barrier film may be a film in which a metal and / or inorganic compound vapor-deposited layer and a coating layer formed from the coating composition are laminated on a synthetic resin film. The thickness of the above gas barrier film is preferably 10 nm to 10 μm. Also,
The gas barrier film using the above synthetic resin film may be formed on the outer surface of the resin layer via an adhesive layer. Next, according to the present invention, a light-emitting portion having an anode, an organic light-emitting layer, and a cathode is formed on an insulating substrate, and the light-emitting portion is covered with an outside air shielding plate, and light is emitted in a gap between the insulating substrate and the outside air shielding plate. Forming a resin layer to surround the portion, sealing the light emitting portion, and
The present invention relates to a method for manufacturing an organic electroluminescent device, comprising forming a gas barrier film comprising a coating composition containing the components (a) and (b) on an outer surface of a resin layer.

[0010]

FIG. 3 is a cross-sectional view schematically showing a structural example of a light emitting portion of a general organic electroluminescent device used in the present invention. In FIG. 3A, on the substrate 1,
An anode 2 is formed, and an organic light emitting layer 3 and a cathode 4 are stacked thereon to form a light emitting section 5. The substrate 1 serves as a support for the organic electroluminescent element, and is made of a plastic film or sheet, a quartz or glass plate, a metal plate or a metal foil, or the like. In particular, a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, and polysulfone, and a glass plate are preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties.
If the gas barrier property of the synthetic resin substrate is low, the organic electroluminescent element may be deteriorated by outside air passing through the substrate, which is not preferable. Therefore, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate to secure gas barrier properties.

An anode 2 is provided on a substrate 1. The anode 2 plays a role of injecting holes into the organic light emitting layer 3. Examples of the material of the anode 2 include conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline, metal oxides such as oxides of indium and / or tin, aluminum, gold, silver, nickel, and the like. Examples include metals such as palladium and platinum, metal halides such as copper iodide, and carbon black. The anode 2 is usually formed by a sputtering method, a vacuum evaporation method, or the like. The anode material is made of fine metal particles such as silver,
In the case of fine particles such as copper iodide, conductive metal oxide fine particles, carbon black, and conductive polymer fine powder,
The anode 2 can also be formed by dispersing in an appropriate binder resin solution and applying it on the substrate 1.

When the anode material is a conductive polymer,
It is also possible to form a thin film directly on the substrate 1 by electrolytic polymerization, or to form an anode 2 by applying a conductive polymer on the substrate 1. The anode 2 can be formed by laminating different substances. The thickness of the anode 2 depends on the required transparency, but is usually 5 to 1,000 nm, preferably 1 to 1,000 nm.
It is about 0 to 500 nm.

The organic light emitting layer 3 formed on the anode 2
It is made of a material that efficiently transports and recombines holes injected from the anode 2 and electrons injected from the cathode 4 between the electrodes to which the electric field is applied, and emits light efficiently by the recombination. The organic light emitting layer 3 can be divided into a hole transport layer 3b and an electron transport layer 3c as shown in FIG.

In the above-described device having the function-separated organic light-emitting layer, the hole transporting layer 3b should have a high hole injection efficiency from the anode 2 and efficiently transport the injected holes. It is preferable that the material can be used. For that purpose, it is preferable that the ionization potential is small, the hole mobility is large, the stability is further improved, and impurities serving as traps are hardly generated at the time of manufacture or use.

Examples of the material of the hole transport layer 3b include a compound in which a pyrenyl group is substituted with a plurality of aromatic diamino groups, an N, N, N-triphenylamine derivative, 1,1-bis (4 -Di-p-tolylaminophenyl) an aromatic diamine compound having a tertiary aromatic amine unit linked thereto, such as cyclohexane, a tertiary amine linked with a fluorene group, or a triphenylbenzene derivative having a starburst structure Triamine, phosphamine derivative, 4,4'-bis [N- (1-naphthyl)
-N-phenylamino] biphenyl and two or more 3
Aromatic amine containing a secondary amine and two or more condensed aromatic rings substituted by nitrogen atoms, triphenylamine derivatives which are sterically asymmetric as a whole molecule, starburst aromatic triamine, tertiary aromatic amine with ethylene group Aromatic diamines having linked units, aromatic diamines having a styryl structure, N, N'-diphenyl-N, N'-bis (3-
Methyl phenyl) Biphenyl-4-4'-diamine or other aromatic diamine thiophene group linked with an aromatic tertiary amine unit, benzylphenyl compound, triamine compound, silazane compound, bisdipyridylaminobiphenyl, diaminophenylphenanthridine Derivatives,
Aromatic diamines having a phenoxazine structure, silanamine derivatives and the like can be mentioned. These compounds can be used alone or in combination of two or more.

In addition to the above-mentioned compounds, materials for the hole transport layer 3b include polyvinyl carbazole, polysilane, polyphosphazene, polymethacrylate containing an aromatic amine, polyvinyl triphenylamine, polyamide,
Polymer materials such as a polymer in which triphenylamine units are linked by a methylene group or the like and a polymer having a triphenylamine skeleton are exemplified.

The hole transport layer 3b is formed by laminating the hole transport material on the anode 2 by a coating method or a vacuum deposition method. In the case of the coating method, one or more hole transport materials and, if necessary, an additive such as a binder resin or a coating improver which does not trap holes are added and dissolved to prepare a coating solution. Then, it is coated on the anode 2 by a method such as spin coating, and dried to form the hole transport layer 3b. Examples of the binder resin include polycarbonate, polyester, and polyarylate. If the amount of the binder resin added is large, the hole mobility is reduced. Therefore, it is desirable that the amount of the binder resin is small, and it is usually preferable that the amount is 50% by weight or less.

In the case of the vacuum evaporation method, the hole transporting material is put into a crucible placed in a vacuum vessel, the inside of the vacuum vessel is evacuated to about 10 ^-4 Pa by a suitable pump, and then the crucible is heated. Then, the hole transport material is evaporated to form a hole transport layer 3b on the anode 2 on the substrate 1 placed facing the crucible. The film thickness of the hole transport layer 3b is usually 10 to 30.
0 nm, preferably 30-100 nm. As described above, in order to uniformly form a thin film, a vacuum deposition method is generally desirable.

Further, the efficiency of hole injection is further improved,
Further, in order to improve the adhesion of the whole organic layer to the anode, as shown in FIG.
The anode buffer layer 3a can also be inserted between the above.
The insertion of the anode buffer layer 3a has the effects of reducing the initial drive voltage of the device and suppressing the voltage rise when the device is continuously driven with a constant current. The characteristics required for the material used for the anode buffer layer are that a uniform thin film can be formed with good contact with the anode, that it is thermally stable, and that the ionization potential is low, and that the hole injection from the anode is difficult. It is easy, and the hole mobility is high.

Therefore, materials used for the anode buffer layer include porphyrin compounds, phthalocyanine compounds, hydrazone compounds, p- (9-anthryl) -N,
Organic compounds such as N-di-p-tolylaniline, star-bust-type aromatic triamine, alkoxy-substituted aromatic diamine derivatives, polythienylenevinylene, poly-p-phenylenevinylene, and polyaniline; sputtering carbon films; ruthenium A metal oxide such as an oxide, a vanadium oxide, or a molybdenum oxide can be used.

Examples of the compound frequently used as the material of the anode buffer layer include a porphine compound and a phthalocyanine compound. These compounds may have a central metal or may be non-metallic. Specific examples of preferred these compounds include porphine, 5,
10,15,20-tetraphenyl-21H, 23H-
Porphine, 5,10,15,20-tetraphenyl-
21H, 23H-porphine copper (II), 5,10,1
5,20-tetraphenyl-21H, 23H-porphine zinc (II), 5,10,15,20-tetraphenyl-21H, 23H-porphine vanadium (IV) oxide, 5,10,15,20-tetraphenyl- 21H,
23H-porphine cobalt (II), 5, 10, 15,
Porphines such as 20-tetra (4-pyridyl) -21H, 23H-porphine; copper (II) 4,4 ′, 4 ″,
And phthalocyanines such as 4 "'-tetraaza-29H, 31H-phthalocyanine, 29H, 31H-phthalocyanine, titanium phthalocyanine oxide, zinc (II) phthalocyanine, lead phthalocyanine, copper (II) phthalocyanine, and magnesium phthalocyanine. In the case of 3a, a thin film can be formed in the same manner as the hole transport layer 3b, and in the case of an inorganic substance, a sputtering method, an electron beam evaporation method, or a plasma CVD method is used.

The thickness of the anode buffer layer 3a is usually
It is 3 to 100 nm, preferably 10 to 50 nm. An electron transport layer 3c is provided on the hole transport layer 3b.
The electron transport layer 3c is formed of a compound capable of efficiently transporting electrons from the cathode in the direction of the hole transport layer 3b between electrodes to which an electric field is applied.

The electron transporting compound used in the electron transporting layer 3c is preferably a compound having a high electron injection efficiency from the cathode 4 and capable of efficiently transporting the injected electrons. Therefore, it is preferable that the compound be a compound having a high electron affinity, a high electron mobility, and having excellent stability and hardly generating impurities serving as traps during production or use.

Materials for the electron transport layer satisfying the above conditions include metal complexes such as 10-hydroxybenzo [h] quinoline metal complex and 8-hydroxyquinoline aluminum complex, p-phenylene compounds, rare earth complexes, Examples include styrylpyrazine derivatives, thiadiazolopyridine derivatives, naphthyridine derivatives, bisstyrylbenzene derivatives, pyrrolopyridine derivatives, and silole derivatives.

In general, the electron transport layer 3c can simultaneously fulfill the role of transporting electrons and the role of providing light emission upon recombination of holes and electrons. When the hole transport layer 3b has a light emitting function, the electron transport layer 3c may only play the role of transporting electrons. For the purpose of improving the luminous efficiency of the device and changing the luminescent color, for example, a fluorescent dye for laser such as coumarin can be doped using an aluminum complex of 8-hydroxyquinoline as a host material.

For the purpose of improving the driving life of the device, it is effective to dope a fluorescent dye with the electron transport layer material as a host material. For example, using a metal complex such as an aluminum complex of 8-hydroxyquinoline as a host material, a naphthacene derivative represented by rubrene,
By doping a condensed polycyclic aromatic ring such as perylene or the like with a quinacridone derivative in an amount of 0.1 to 10% by weight with respect to the host material, it is possible to greatly improve the light-emitting characteristics of the device, particularly the driving stability.

The thickness of the electron transport layer 3c is usually 10 to 2
00 nm, preferably 30 to 100 nm. The electron transporting layer 3c can be formed by the same method as the hole transporting layer 3b, and usually, a vacuum evaporation method is used. Note that FIG.
As the single-layer type organic light emitting layer 3 which does not perform the function separation as in (A), the above poly (p-phenylenevinylene) and poly [2-methoxy-5- (2-ethylhexyloxy)
[-1,4-phenylenevinylene], a polymer material such as poly (3-alkylthiophene), a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole, and the like.

As a method for further improving the luminous efficiency of the organic electroluminescent device, an electron injection layer (not shown) can be further laminated on the organic luminescent layer 3. The material used for the electron injection layer is required to be capable of easily injecting electrons from the cathode and having a higher electron transport ability. Examples of such an electron transporting material include the oxadiazole derivative, the aluminum complex of 8-hydroxyquinoline, the system in which they are dispersed in a resin such as polymethyl methacrylate (PMMA), and n-type hydrogen. Amorphous silicon carbide, n-type zinc selenide, n-type zinc sulfide, 2-t-butyl-9,10-N, N'-dicyanoanthraquinone diimine, a phenanthroline derivative and the like. The thickness of the electron injection layer is usually 5 to 200 n.
m, preferably 10 to 100 nm.

The cathode 4 plays a role of injecting electrons into the organic light emitting layer 3. The material used for the cathode 4 may be the same as the material for the anode 2. For efficient electron injection, a metal having a low work function is preferable. As a material for the cathode, a suitable metal such as indium, magnesium, tin, calcium, aluminum, silver, silver, lithium, or an alloy thereof is used.

For example, a low work function alloy electrode such as a magnesium-silver alloy, an aluminum-lithium alloy, and a magnesium-indium alloy may be used. Furthermore, the cathode 4
Li _{2 is applied to} the interface between the organic light emitting layer 3 and the electron transport layer 3c.
Inserting an ultrathin film (0.1 to 5 nm) such as O or LiF is also an effective method for improving the efficiency of the device. The thickness of the cathode 4 is usually the same as that of the anode 2. Further laminating a metal layer having a high work function and being stable to the atmosphere for the purpose of protecting the cathode made of the low work function metal increases the stability of the device. For this purpose, metals such as aluminum, nickel, chromium, silver, gold, platinum and the like are used.

In the present invention, a structure reverse to that of FIG. 3A, that is, a cathode 4, an organic luminescent layer 3, and an anode 2 can be laminated on a substrate in this order, as described above. It is also possible to provide the organic electroluminescent device of the present invention between two substrates, at least one of which is highly transparent. Similarly, the layers can be stacked in a structure opposite to the above-described layers shown in FIGS. 3B and 3C.

In the present invention, it is necessary to seal the whole element in order to improve the stability and reliability (durability) of the organic electroluminescent element. Hereinafter, the organic electroluminescent device of the present invention will be described with reference to FIGS.

Since the cathode of the organic electroluminescent device has a low work function, it is oxidized particularly by moisture, and the oxidized portion becomes high in resistance or peels off from the organic layer. For this reason, the organic electroluminescent element tends to generate a dark spot. Therefore, in order to suppress the dark spot, first, the element must be placed in an airtight structure in which the light emitting unit 5 blocks moisture from the outside air. As a specific method of sealing the light emitting unit 5 in the hermetic structure, a plate-shaped or sheet-shaped outside air shielding plate 6 having gas barrier properties is placed facing the insulating substrate 1 supporting the light emitting unit 5, The resin 7 is applied so as to surround the periphery of the light emitting unit 5, and is bonded and sealed. As the outside air shielding plate 6, those described above as the insulating substrate 1 can be used, and a metal plate, a metal foil, a quartz or glass plate, a plastic film or a sheet, or the like is used.

In particular, as the outside air shielding plate 6, a glass plate or a transparent synthetic resin plate such as polyester, polymethyl methacrylate, polycarbonate, and polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties, and it is desirable to provide a dense silicon oxide film on at least one surface of the synthetic resin substrate to ensure gas barrier properties. Insulating substrate 1 and outside air shielding plate 6
The resin layer 7 is used for bonding. As a material used for the resin layer 7, an epoxy resin is preferable in consideration of gas barrier properties. Here, as the epoxy-based resin, a light-curing type and a thermosetting type are exemplified. As a photocurable epoxy resin, 30Y manufactured by Three Bond Co., Ltd.
-184G, and XNR5493T manufactured by Chise Nagase. In addition, as thermosetting epoxy resin,
XNR5155 manufactured by Nagase Chiba Co., Ltd. and the like.
In addition, room temperature curing type Araldite or modified epoxy elastic adhesive manufactured by Ciba Geigy Co., Ltd., for example, EP-001 manufactured by Cemedine Co., Ltd., MOS7 manufactured by Konishi Co., Ltd., and vacuum adhesive manufactured by Varian Co., Ltd. Torr Se
al and the like.

The moisture permeability of the resin layer 7 is 10 cc / m ²
Atm · 24 hr (JIS Z0208), which is insufficient for practical use, and the gas barrier properties aimed at by the present invention are insufficient. In the present invention, as shown in FIG. 1, a gas barrier film 8 having excellent gas barrier properties (external air moisture blocking properties) is provided outside the resin layer 7. FIG. 2 shows FIG. 1 as viewed from above (outside air shielding plate). Reference numeral 9 denotes a portion where the resin layer 7 is provided on the outer peripheral portion of the light emitting body 5, and the gas barrier film 8 is provided outside the portion. Reference numeral 2a indicates an anode extraction electrode portion, and reference numeral 4a indicates a cathode extraction electrode portion. The gas barrier film 8 is formed in such a manner as to leave contact portions with these external circuits.

In the present invention, as described above, the gas barrier film 8 is formed on a gas barrier film composed of a coating composition containing the components (a) and (b) and a synthetic resin film. On a gas barrier film composed of a gas barrier coating film having a coating layer formed thereon, or a synthetic resin film, a metal and / or inorganic compound vapor-deposited layer and a coating layer formed from the coating composition were laminated. A gas barrier film composed of a gas barrier coating film is used. Hereinafter, the coating composition and the gas barrier coating film constituting the gas barrier film used in the present invention will be described.

Coating composition (a) component: The ethylene / vinyl alcohol copolymer used as the component (a) in the present invention is a saponified product of a copolymer of ethylene and vinyl acetate, that is, ethylene-vinyl acetate. It is obtained by saponifying a random copolymer, and is obtained from a partially saponified product in which acetic acid groups remain in tens of mol%, from complete saponification in which only a few mol% of acetic acid groups remain or acetic acid groups do not remain. Although not particularly limited, the preferred degree of saponification is 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. Content of repeating units derived from ethylene in ethylene / vinyl alcohol copolymer (hereinafter also referred to as "ethylene content")
Is usually 20 to 50 mol%, preferably 25 to 45 mol%. Specific examples of the ethylene / vinyl alcohol copolymer include EVAL EP-F manufactured by Kuraray Co., Ltd.
101 (ethylene content; 32 mol%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 2
9 mol%), Soarnol D2935 (ethylene content; 2
9 mol%).

The melt flow index of the above-mentioned (a) ethylene / vinyl alcohol copolymer is 1 to 50 g / 10 minutes at 210 ° C. under a load of 21.168 N. These (a) ethylene / vinyl alcohol copolymers can be used alone or in combination of two or more.

The ethylene / vinyl alcohol copolymer constituting the component (a) is itself excellent in gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like. In addition, when the ethylene-vinyl alcohol copolymer cures a coating film obtained from the composition of the present invention, a hydroxyl group present in a repeating unit derived from polyvinyl alcohol has a component (b) described below and / or By co-condensing with the component (c), excellent coating film performance can be provided.

The proportion of the component (a) in the coating composition of the present invention is 10 to 10,000 parts by weight, preferably 20 to 5, based on 100 parts by weight of the component (b) described below.
000 parts by weight, more preferably 100 to 1,000 parts by weight. If the amount is less than 10 parts by weight, cracks easily occur in the obtained coating film, and the gas barrier property is reduced.
If the amount exceeds 000 parts by weight, the resulting coating film is unfavorably reduced in gas barrier properties under high humidity.

Component (b): Component (b) used in the present invention is a metal alcoholate, a hydrolyzate of the metal alcoholate, or a condensate of the metal alcoholate represented by the above general formula (1). A chelate compound of the metal alcoholate (hereinafter also referred to as “metal chelate compound”), a hydrolyzate of the metal chelate compound, a condensate of the metal chelate compound, a metal acylate, a hydrolyzate of the metal acylate,
And at least one selected from the group of condensates of the metal acylate. That is, the component (b)
Only one of the species may be used, or a mixture of any two or more species may be used. Further, the metal chelate compound is a metal alcoholate and at least one compound selected from β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxylates, keto alcohols and amino alcohols (Hereinafter also referred to as "chelating agent"). Among these chelating agents, it is preferable to use β-diketones or β-ketoesters,
Specific examples of these include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, and t-acetoacetate. Butyl, 2,4-hexane-dione, 2,4-heptane-
Examples thereof include dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Here, the hydrolyzate of the metal alcoholate, a hydrolyzate of the metal chelate compound, and hydrolyzate of the metal acylate is not necessarily OR ² group is all hydrolysed contained in the metal alcoholate For example, one in which only one is hydrolyzed, one in which two or more are hydrolyzed, or a mixture thereof may be used. The condensate of the metal alcoholate, the condensate of the metal chelate compound, and the condensate of the metal acylate are formed by condensing the metal alcoholate, the metal chelate compound, and the M-OH group of the hydrolyzate of the metal acylate. However, in the present invention, it is not necessary that all M-OH groups are condensed, and only a small part of M-OH
It is a concept that includes those in which groups are condensed, those having different degrees of condensation, and mixtures of condensates in which M-OR groups and M-OH groups are mixed. When a condensate is used as the component (b), the above-mentioned metal alcoholate,
The metal chelate compound and the metal acylate which have been hydrolyzed and condensed in advance may be used, or a commercially available condensate may be used. Further, a condensate of a metal alcoholate may be used as it is, or may be reacted with the above chelating agent and used as a condensate of a metal chelate compound. Commercially available condensates of the above metal alcoholates include A-1 manufactured by Nippon Soda Co., Ltd.
0, B-2, B-4, B-7, B-10 and the like.
It is considered that the component (b) functions to form a co-condensate with the component (a).

As the metal atom represented by M in the above general formula (1), zirconium, titanium and aluminum can be mentioned as preferred, and titanium is particularly preferred. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. When it is a metal alcoholate, for example, methyl, ethyl, n-propyl, i-propyl, n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acetyl group, propionyl group, butyryl group , Valeryl group, benzoyl group, acyl group such as trioil group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy, ureido, amide, fluoracetamide, and isocyanate groups,
Substituted derivatives of these groups can be mentioned. R
Examples of the substituent in the substituted derivative ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group,
-An epoxycyclohexyl group, a (meth) acryloxy group, a ureido group, an ammonium base and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. In the case of a metal acylate, R ¹ has 1 to ¹ carbon atoms.
As the monovalent organic group of 8, an acetoxyl group, a propionyloxyl group, a butylyloxyl group, a valeryloxyl group,
An acyloxyl group such as a benzoyloxyl group and a trioyloxyl group can be exemplified. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, sec-butyl group, t
-Butyl group, n-pentyl group and the like,
Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group,
Examples include a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R ² in the general formula (1) may be the same or different from each other.

Specific examples of the metal alcoholate and the chelate compound of the metal alcoholate among the components (b) include (a) tetra-n-butoxyzirconium and tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. A zirconium compound;

(B) Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, dihydroxybislactatetitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C) Aluminum tri-i-propoxy, aluminum di-i-propoxy ethyl acetoacetate, aluminum di-i-propoxy acetylacetonate, aluminum i-propoxy bis (ethyl acetoacetate), i-propoxy Aluminum compounds such as bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonate bis (ethylacetoacetate) aluminum; Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxy. Bis (triethanolaminate) titanium, dihydroxybislactatetitanium titanium, di-i-propoxyethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum can be mentioned, and particularly preferred compounds are di-i-propoxy. Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, and dihydroxybislactatetotitanium;

Further, specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimallonate, di-i-propoxy titanium dibenzoylate, di -N-butoxy-zirconium diacetate, di-i-propylaluminum monomalonate, etc., and particularly preferred compounds are dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These components (b) are used alone or in combination of two or more.

As the component (b), since the viscosity of the coating solution does not change with time and is easy to handle, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent described in a hydrophilic solvent described below. It is preferable to use those subjected to a decomposition treatment. By performing such a hydrolysis treatment before mixing with the component (a), the unhydrolyzed component (b), partially hydrolyzed component (b), and partially condensed component (b) The mixture becomes a mixture, and a sharp increase in viscosity due to a shock or the like that occurs when the composition is mixed with the component (a) during preparation of the composition, and an increase in viscosity over time are suppressed. in this case,
The amount of water used is 0.1 mol per mol of R ¹ _mM (OR ² ) _n.
１，1,000 mol, preferably 0.5-500 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is such that water / hydrophilic organic solvent = 10-90 / 90-10
(Weight ratio), preferably 20-80 / 80-20, more preferably 30-70 / 70-30. As the component (b), particularly preferred are di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium,
It is obtained by hydrolyzing a titanium compound such as dihydroxybislactate-titanium with the above-mentioned mixed solvent.

The coating composition of the present invention preferably contains a nitrogen-containing organic solvent as required. Examples of the nitrogen-containing organic solvent include hydrophilic nitrogen-containing organic solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, and pyridine; thymine, glycine, cytosine, and guanine. Nucleic acid bases; hydrophilic nitrogen-containing polymers such as polyvinylpyrrolidone, polyacrylamide, and polymethacrylamide; and copolymers obtained by copolymerizing these components. Of these, N, N-dimethylacetamide, N, N-dimethylformamide and polyvinylpyrrolidone are preferred. By mixing a nitrogen-containing organic solvent, a coating film having a better appearance and a better appearance in thin film coating can be obtained, and inorganic particles and / or
Alternatively, it exerts a catalytic effect when condensing with an inorganic laminate. The proportion of the nitrogen-containing organic solvent used in the total amount of the solvent,
Preferably it is 0 to 70% by weight, more preferably 1 to 50% by weight.
%, Particularly preferably 5 to 50% by weight.

Component (c): The coating composition of the present invention preferably contains inorganic fine particles as the component (c). The inorganic fine particles are a particulate inorganic substance having an average particle diameter of 0.2 μm or less and substantially containing no carbon atoms,
Metal or silicon oxide, metal or silicon nitride, metal boride. Methods for producing inorganic fine particles include, for example, a gas phase method in which silicon tetrachloride is obtained by hydrolysis of oxygen and hydrogen in a flame to obtain silicon oxide, a liquid phase method in which sodium silicate is ion-exchanged, a silica gel mill, and the like. Production methods such as solid phase method obtained by pulverization by,
It is not limited to these methods.

Specific examples of the compound include SiO_Two, A
l_TwoO_Three, TiO_Two, WO_Three, Fe _TwoO_Three, ZnO, N
iO, RuO_Two, CdO, SnO_Two, Bi_TwoO_Three, 3A
l_TwoO_Three・ 2SiO_Two, Sn-In_TwoO_Three, Sb-In
_TwoO_Three, Oxides such as CoFeOx, Si_ThreeN_Four, Fe
_FourNitrides such as N, AlN, TiN, ZrN, TaN,
Ti_TwoB, ZrB_Two, TaB_Two, W_TwoBorides such as B
Is mentioned. The form of the inorganic fine particles may be powder, water, or the like.
Or colloids or sols dispersed in organic solvents.
However, these are not limited. Among these
To co-condensate with component (a) and / or component (b)
In order to obtain excellent coating performance by
Idal silica, colloidal alumina, alumina sol,
Sol, zirconium sol, antimony pentoxide sol, acid
Cerium oxide sol, zinc oxide sol, titanium oxide sol, etc.
Colloidal oxides with hydroxyl groups on the particle surface
It is. The average particle diameter of the inorganic fine particles is preferably 0.2 μm or less.
It is preferably 0.1 μm or less, and the average particle size is 0.2 μm
If it exceeds, the gas barrier property is inferior from the viewpoint of the denseness of the film.
There are cases.

The proportion of the component (c) in the composition of the present invention is as follows:
Preferably 0 to 900 parts by weight, particularly preferably 2 parts by weight, per 100 parts by weight of the total amount of the components (a) and (b).
0 to 400 parts by weight. If the amount exceeds 900 parts by weight, the gas barrier properties of the resulting coating film may decrease.

Optional component: (d) a curing accelerator is used for the purpose of curing the composition of the present invention more quickly and for the purpose of easily forming a cocondensate of the component (a) and the component (b). The curing at a relatively low temperature and the use of this curing accelerator (d) are more effective in order to obtain a denser coating film.

The (d) curing accelerator includes inorganic acids such as hydrochloric acid; naphthenic acid, octylic acid, nitrous acid, sulfurous acid,
Alkali metal salts such as aluminate and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide; acidic compounds such as alkyltitanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid and phthalic acid; ethylenediamine, hexanediamine , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2- aminoethyl) - aminopropyl trimethoxysilane, .gamma. (2-aminoethyl) - aminopropyl methyl dimethoxy silane, amine compounds such as .gamma. anilino trimethoxysilane, (C ₄ H _{9) 2 n (OCOC 11 H 23) 2} , (C 4
H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ ,
(C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC
_{4 H 9) 2, (C} 8 H 17) 2 Sn (OCOC
_{11 H 23) 2, (C} 8 H 17) 2 Sn (OCOCH = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOCC)
Carboxylic acid type organotin compounds such as ₈ H ₁₇ ) ₂ ; (C ₄
H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H
₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C
_{8 H 17) 2 Sn (SCH} 2 COOC 8 H 17) 2, (C 8
_{H 17) 2 Sn (SCH 2} CH 2 COOC 8 H 17) 2,
(C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ ,
(C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ ,

[0055] Mercaptide-type organotin compounds such as; Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
nO, or (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
An organic tin compound such as a reaction product of an organic tin oxide such as nO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate is used. The proportion of these (d) curing accelerators in the composition is usually 0 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the solid content of the composition of the present invention. .

Further, the composition of the present invention may contain, as a stability improver, β-diketones and / or β-diketones described above.
-Ketoesters can be added. That is,
By coordinating to a metal atom in the metal alcoholate present in the composition as the component (b), the composition acts to control the condensation reaction between the component (a) and the component (b), and the composition obtained It is considered that they act to improve the storage stability of the product. β-diketones and / or β
The amount of the ketoester to be used is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (b).

The coating composition of the present invention is usually obtained by dissolving and dispersing the above components (a) and (b) and optionally the above optional components in water and / or a hydrophilic organic solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, and se.
c-butyl alcohol, tert-butyl alcohol,
1 carbon atoms such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol, etc.
Saturated aliphatic monohydric alcohol or dihydric alcohol having from 8 to 8 carbon atoms such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate;
A saturated aliphatic ether compound having 1 to 8 carbon atoms, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoether acetate, ethylene glycol monobutyl ether acetate;
Ester compounds of polyhydric alcohols; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate,
Examples thereof include hydroxycarboxylic acids or hydroxycarboxylic acid esters such as salicylic acid and methyl salicylate. Of these, preferred are
1 to 1 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol
And 8 saturated aliphatic monohydric alcohols.

These water and / or hydrophilic organic solvent are more preferably used by mixing water and a hydrophilic organic solvent. The preferred solvent composition is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms and water / nitrogen-containing organic solvent. More preferably, water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing organic solvent.
By mixing a nitrogen-containing organic solvent, a good coating film having a transparent appearance in a thin film coating can be obtained.

The amount of water and / or hydrophilic organic solvent used is such that the total solid content of the composition is preferably 60% by weight or less. For example, when it is used for forming a thin film, it is usually 5 to 40% by weight, preferably 10 to 30% by weight, and when it is used for forming a thick film, it is usually 20 to 50% by weight. %, Preferably 30
~ 45% by weight. When the total solid content of the composition exceeds 60% by weight, the storage stability of the composition tends to decrease.

As the organic solvent, the above-mentioned water and / or hydrophilic organic solvent is preferable. In addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, tetrahydrofuran, dioxane, etc. Ethers, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

As described above, the coating composition of the present invention is obtained by mixing the above components (a) and (b) and optionally the above optional components in water and / or a hydrophilic organic solvent. Is obtained by hydrolyzing and / or condensing the above components (a) and (b) and, if necessary, component (c) in water and / or a hydrophilic organic solvent. In this case, the reaction conditions are such that the temperature is 20 to 100 ° C, preferably 30 to 80 ° C, and the time is 0.1 to 20 hours, preferably 1 to 10 hours.

The coating composition of the present invention includes:
A filler may be separately added and dispersed in order to develop various properties such as coloring, thickening of the obtained coating film, prevention of ultraviolet transmission to the base, imparting corrosion resistance, and heat resistance. However, the filler excludes the component (c). As the filler, for example, organic pigments, other than water-insoluble pigments or pigments such as inorganic pigments, particulate, fibrous or flaky metals and alloys and oxides and hydroxides thereof,
Carbides, nitrides, sulfides and the like. Specific examples of the filler include particles, fibrous or scaly,
Iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide,
Titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, Talc, barium carbonate, calcium carbonate,
Magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine, navy blue, pigment green, rock ultramarine, Cobalt blue, Cerulean blue, Copper borate, Molybdenum blue, Copper sulfide, Cobalt purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium plumbate, Zinc yellow, Lead sulfide, Chrome yellow, Loess, Cadmium yellow, Strontium Yellow, titanium yellow, litharge,
Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red, Chrome Vermillion, Bengala, Zinc White, Antimony White, Basic Lead Sulfate, Titanium White, Lithopon, Lead Silicate,
Zircon oxide, tungsten white, lead zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. Can be

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100 to 50,000 nm.
５，5,000 nm. The proportion of the filler in the composition is
Preferably 0.1 to 300 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the total solids of the components other than the filler.
00 parts by weight.

The coating composition of the present invention includes:
Other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants,
Additives other than those described above, such as a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be blended.

In preparing the coating composition of the present invention, the above components (a) and (b), preferably (a)
A composition containing the components (b) to (c) may be prepared. Preferably, the component (b) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then the component (a) is hydrolyzed. Mix. In this case, there is no change in viscosity of the coating composition over time, and a coating composition excellent in handleability can be obtained. Specific examples of the method for preparing the coating composition of the present invention when the component (c) is used include the following. The component (b) used in these preparation methods may be one which has been hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (c) is added to the components, and then the component (b) is added. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (c) is added to the components, and then the component (b) is added, followed by hydrolysis and / or condensation. (A) dissolved in water and / or a hydrophilic organic solvent
A method in which the component (b) is added to the components, hydrolysis and / or condensation is performed, and then the component (c) is added. A method in which the components (a) to (c) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Alternatively, a method of performing hydrolysis and / or condensation thereafter.

Coating Film The coating composition used in the present invention is applied directly to the resin layer 7 or applied to a synthetic resin film to be used as the gas barrier film 8. That is, when a coating film is obtained, a coating layer comprising the coating composition of the present invention or a coating layer comprising a vapor deposition layer of a metal and / or an inorganic compound and a coating composition of the present invention is formed on a synthetic resin film. By laminating the film layers, a coating film having excellent gas barrier properties can be obtained. By laminating this film on the outer surface of the resin layer 7, a gas barrier film can be formed.

Here, the synthetic resin film is a sheet or film, and is made of polyethylene,
Polyolefin such as polypropylene; Polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate; Nylon 6, Nylon 6,6, Nylon 4,6, Nylon 1
2 such as polyamide, polyvinyl chloride, polyvinyl alcohol, aromatic polyamide, polyamide imide, polyether imide, polysulfone, polyether sulfone, polyether ketone, polyarylate, polyphenylene sulfide, polyphenylene oxide, tetrafluoroethylene, trimonochloride A sheet or film used as a packaging material such as fluoroethylene, fluoroethylene-propylene copolymer, and polyimide can be used. These synthetic resin films, if necessary,
Biaxially stretched films can also be used. In addition, additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a coloring agent can be added to the synthetic resin film.

Further, a known surface activation treatment such as corona discharge treatment, plasma activation treatment, glow discharge treatment, reverse sputtering treatment, surface roughening treatment, etc. It is also possible to perform primer treatment with a primer agent such as an imine-based, amine-based, epoxy-based, urethane-based, or polyester-based primer. The thickness of the synthetic resin film is not particularly limited, but is usually 5 to 100 μm, preferably 10 to 50 μm.

A coating layer formed from the coating composition of the present invention (hereinafter also referred to as “coating of the present invention”) on a substrate such as the resin layer 7 or a synthetic resin film (hereinafter also referred to as a “substrate”). Is laminated on the surface of the substrate by a coating method such as a roll coat such as a microgravure coater, a spray coat, a spin coat, a dipping, a brush, a bar code, an applicator, etc. A coating film of the present invention having a thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed, and can be formed at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C. under a normal environment. By heating and drying for 5 to 60 minutes, preferably 1 to 10 minutes, condensation is performed, and the coating film of the present invention can be formed.

At this time, it is also possible to laminate a metal and / or inorganic compound vapor-deposited layer (hereinafter also referred to as a “vapor-deposited layer”) on the substrate or the coating film of the present invention. By providing this vapor deposition layer, the gas barrier property is further improved. Here, aluminum,
Silicon, titanium, zinc, zirconium, magnesium,
Metals such as tin, copper, and iron, and oxides, nitrides, sulfides, and fluorides of these metals such as aluminum oxide, silicon dioxide, titanium oxide, zirconium oxide, magnesium oxide, tin oxide, zinc sulfide, and fluoride. Magnesium oxide or the like is used.

As a method of forming the vapor deposition layer, a vapor deposition method such as vacuum vapor deposition, ion plating, and sputtering is used, but vacuum vapor deposition and ion plating are preferable from the viewpoint of production efficiency. The inside of the vapor deposition device is 2 × 10 ^-6 to 8 ×
10 ^-3 Torr (2.7 × 10 ^{-4 to} 1.07 Pa), preferably 8 × 10 ^-6 to 8 × 10 ^-5 Torr (1.1 × 1
After evacuation to 0 ^{-3 to} 1.1 × 10 ^-2 Pa), a vapor deposition process is performed. This vapor-deposited layer has a barrier property against oxygen and water vapor, but aluminum, silicon oxide, aluminum oxide and the like are particularly excellent in gas barrier property. The film thickness of the vapor deposition layer is 1 to 500 nm, preferably 3 to 300 nm. If it is less than 1 nm, the gas barrier property may not be sufficient. On the other hand, if it exceeds 500 nm, the flexibility of the vapor deposition layer is impaired, and cracks and Pinholes are more likely to occur,
Both have poor gas barrier properties. The above-mentioned vapor deposition layer may use a plurality of vapor deposition materials in combination, or may have two or more layers.

Specific examples of the method for forming the gas barrier film of the present invention using the coating composition of the present invention include:
The following methods are mentioned. Substrate (resin layer or synthetic resin film, same hereafter)
A method for forming a coating film of the present invention on a surface. If necessary, a primer of the present invention may be applied in advance on the surface of the substrate to form the coating film of the present invention. A method for forming a vapor-deposited layer on the surface of a substrate and forming the coating film of the present invention on the surface of the vapor-deposited layer. When forming a vapor deposition layer on the surface of the substrate, a primer may be applied in advance on the surface of the substrate, if necessary. A method for forming a vapor-deposited layer on the coating film surface of the present invention as described above. A method for forming a vapor-deposited layer on the coating film surface of the present invention as described above. A method for forming a coating film of the present invention on the surface of the above-mentioned vapor deposition layer. A method for forming a coating film of the present invention on the surface of the above-mentioned vapor deposition layer. The method of the above-mentioned, wherein the surface of the substrate is one side or both sides.

When a gas barrier film composed of the above-mentioned gas barrier coating film is laminated on the outer surface of the resin layer, it is effective to insert an adhesive layer in order to enhance the adhesion between the resin layer and the gas barrier film. . Examples of the adhesive layer include polysiloxane represented by a composition formula of SiOx (x is less than 1), vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, and rubber. System, other solvent type,
Aqueous type and emulsion type are mentioned. The thickness of the adhesive layer is usually 0.1 to 10 μm, preferably 0.5 to 5 μm.

[0075]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Various measurements in Examples and Comparative Examples were performed by the following methods.

[0076] oxygen permeability manufactured by Modern Controls, Inc., MOCON OXTRAN2
/ 20 was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 90 RH%. Viscosity of coating liquid The viscosity at a liquid temperature of 25 ° C. was measured by a B-type viscometer. The viscosity measurement was performed immediately after the preparation of the coating composition and 24 hours later.

Reference Example 1 (Preparation of Titanium Chelate Compound) To a reactor equipped with a reflux condenser and a stirrer, 100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added, and the mixture was stirred at 60 ° C. for 30 minutes. The compound was obtained. The purity of the reaction product was 75%.

Reference Example 2 (Preparation of Coating Composition) As the component (a), an ethylene / vinyl alcohol copolymer [manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol D2935, degree of saponification: 98% or more, ethylene content: 29 mol] %, Melt flow index; 35 g / 10 min], 5% water / n-
100 parts of a propyl alcohol solution (water / n-propyl alcohol weight ratio = 4/6), 2 parts of the titanium chelate compound prepared in Reference Example 1 as the component (b), 16.8 parts of n-propyl alcohol and water 11.2 Mix the parts,
A coating composition of the present invention was obtained. The viscosity immediately after the preparation of the composition was 15 mPa · s. Next, a 40 nm-thick inorganic compound vapor-deposited layer was formed on a 12 μm-thick polyethylene terephthalate (PET) film by a vacuum vapor deposition method using silicon dioxide as a vapor deposition source. The composition obtained above was coated on the polyethylene terephthalate (PET) film subjected to corona discharge treatment with a bar coater, and heated at 100 ° C. with a hot air drier at 10 ° C.
After drying for 1 minute, a coating film having a thickness of 1.0 μm was formed to obtain a gas barrier coating film. The oxygen permeability of this film is 0.05 cc / m ² · atm at 90% humidity.
-It was 24 hours.

Example 1 An organic electroluminescent device having a light-emitting portion structure shown in FIG. 3C was manufactured according to the description in JP-A-11-144864. That is, a transparent conductive film of indium tin oxide (ITO) deposited on a glass substrate to a thickness of 120 nm (manufactured by Geomatic Corporation; electron beam film-formed product; sheet resistance 15)
Ω) was patterned into a 2 mm-wide stripe using ordinary photolithography and hydrochloric acid etching to form an anode. The pattern-formed ITO substrate is cleaned in the order of ultrasonic cleaning with acetone, water cleaning with pure water, and ultrasonic cleaning with isopropyl alcohol, and then dried under a nitrogen stream. It was installed in. After the above device is evacuated by an oil rotary pump, an oil diffusion pump equipped with a liquid nitrogen trap is used until the degree of vacuum in the device becomes 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less. And evacuated. Copper phthalocyanine (crystal form is β-type) placed in a molybdenum boat placed in the above-described apparatus was heated to perform vapor deposition. Vacuum 2 ×
10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa), deposition time 1
The anode buffer layer 3a having a thickness of 20 nm was obtained.

Next, the ceramics placed in the device
4,4'-bis [N- (1-naphthy
Ru) -N-phenylamino] biphenyl around the crucible
Was heated with a tantalum wire heater to perform vapor deposition. This and
The temperature of the crucible is controlled in the range of 250-260 ° C.
Was. Degree of vacuum 1.7 × 10 during evaporation^-6Torr (about 2.3
× 10^-FourPa), a deposition time of 3 minutes and 30 seconds and a film thickness of 60 nm.
The hole transport layer 3b was obtained. An electron with a light-emitting function
As a host material of the transport layer 3c, aluminum 8-h
Droxyquinoline complex [Al (C ₉H₆NO)_Three]
Rubrene as a soup pigment, each with a separate crucible
Was used to perform binary deposition.

At this time, the crucible temperature of the 8-hydroxyquinoline complex of aluminum is controlled in the range of 270 to 300 ° C., the crucible temperature of rubrene is controlled in the range of 150 to 160 ° C., and the degree of vacuum during vapor deposition is 1.3 ×. 10 ⁻⁶ Torr (about 1.7 × 10 ⁻⁴ Pa), the deposition time was 3 minutes and 10 seconds, and the thickness of the deposited electron transport layer was 75 nm. The above-described anode buffer layer 3a, hole transport layer 3b, and electron transport layer 3
The substrate temperature when vacuum-depositing c was kept at room temperature.

Here, vapor deposition up to the electron transport layer 3c is performed.
Once removed element from the vacuum evaporation system to the atmosphere
2 mm wide stripes as a mask for cathode deposition
Make the shadow mask orthogonal to the ITO stripe of anode 2.
In a vacuum deposition apparatus
And the degree of vacuum in the apparatus is 2 × 10 ^-6
Torr (about 2.7 × 10^-FourExhaust until below Pa)
did. Then, as the cathode 4, an alloy of magnesium and silver
The electrode is made to have a thickness of 44 nm by a binary simultaneous evaporation method.
Was deposited. Vapor deposition using molybdenum boat
1 × 10^-FiveTorr (about 1.3 × 10^-3Pa), during evaporation
For 3 minutes and 20 seconds. Also, the atoms of magnesium and silver
The ratio was 10: 1.4. Subsequently, the vacuum of the device is reduced.
Do not break the aluminum using a molybdenum boat
Laminated on a magnesium-silver alloy film with a thickness of 40 nm
Thus, the cathode 4 was completed. The degree of vacuum during aluminum deposition
1.5 × 10^-FiveTorr (about 2.0 × 10^-3Pa), steam
The wearing time was 1 minute and 20 seconds. More magnesium and silver
The substrate temperature during the deposition of a two-layer cathode of alloy and aluminum is
It was kept at room temperature.

As described above, an organic electroluminescent device having a size of 2 mm × 2 mm was obtained. After the device was taken out of the cathode vapor deposition device, the device was sealed according to the structure shown in FIGS. First, after replacing the evaporation mask with a shadow mask that covers the entire element part, the above element is installed again in the above-described cathode evaporation apparatus, and the GeO film is placed on the cathode 4 in the same manner as described above. Film thickness 2
Lamination was performed at 00 nm to form a protective layer. At this time, the degree of vacuum was 1.5 × 10 ⁻⁶ Torr (about 2.0 × 10 ⁻⁴ ), the deposition time was 5 minutes, and the substrate temperature was room temperature. Take the element out of the above device to the atmosphere and use the same material and
Photocurable resin on the glass plate of the thickness [Corporation ThreeBond Ltd., 30Y-184G] was applied to the element peripheral portion as shown in FIG. 1, cured by 4J / cm ² irradiation exposure with a high pressure mercury lamp Was.

The coating composition prepared in Reference Example 2 was applied to the outer periphery of the photo-cured resin of the device sealed with the photo-cured resin by a bar coater, and was then heated to 100 ° C. by a hot air drier.
For 10 minutes to form a coating film (gas barrier film) having a thickness of 2.0 μm. When the gas barrier film was laminated on this photocurable resin layer, the moisture permeability was 90% and 0.04%.
5cc / m ² · atm · 24hr (JIS Z020
8).

The organic electroluminescent device thus obtained was left in an environmental tester set at a temperature of 80 ° C. and a relative humidity of 90%, and the light emission luminance and the area of the dark spot were measured. The brightness and the voltage are values at a current drive of 15 mA / cm ² . For the measurement of the dark spot, the light emitting surface of the element was photographed with a CCD camera, and then binarized by image analysis to quantify. Table 1 shows the measured changes over time. The growth of dark spots could be suppressed to a level that would not be a problem in practical use.

[0086]

[Table 1]

Comparative Example 1 A sealing element was produced in the same manner as in Example 1 except that no gas barrier layer was provided. Table 2 shows the results of the environmental test at 80 ° C.-90%. After storage for 48 hours, many dark spots having a diameter of 250 μm were generated.

[0088]

[Table 2]

[0089]

According to the organic electroluminescent device of the present invention, a specific gas barrier layer can be formed on a sealing resin layer by a simple means,
It is possible to obtain a sealing element that exhibits stable light emission characteristics during storage and driving without being affected by moisture in the atmosphere. Therefore, the organic electroluminescent device according to the present invention can be used as a light source (for example, for a copier) for a flat panel display (for example, for an OA computer or a wall-mounted television), an in-vehicle display device, a mobile phone display, and a surface light emitter. Light sources, backlight sources for liquid crystal displays and instruments), display panels,
It can be applied to beacon lights, and its technical value is great.

[Brief description of the drawings]

FIG. 1 is a schematic longitudinal sectional view showing an example of the organic electroluminescent device of the present invention.

FIG. 2 is a plan view of the organic electroluminescent device of FIG.

FIG. 3 is a longitudinal sectional view showing a structure of a light emitting unit.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Organic light emitting layer 4 Cathode 5 Light emitting part 6 Outside air shielding plate 7 Resin layer 8 Gas barrier film

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05B 33/14 H05B 33/14 A 33/22 33/22 BD // C08L 101: 00 C08L 101: 00 F term (reference) 3K007 AB11 AB13 AB18 BA06 BB01 CA01 CB01 DA01 DB03 EA01 EB00 FA02 4F006 AA11 AA31 AA34 AB20 AB64 BA05 CA08 DA04

Claims (8)

[Claims] An insulating substrate, a light emitting portion having an anode, an organic light emitting layer, and a cathode formed on the insulating substrate, and an outside air shielding plate covering the light emitting portion, wherein the insulating substrate and the outside air A resin layer is formed so as to surround the light emitting portion in the gap with the shielding plate to seal the light emitting portion, and on the outer surface of the resin layer,
An organic electroluminescent device comprising a gas barrier film formed of a coating composition containing the following components (a) and (b). (A) Ethylene / vinyl alcohol copolymer (b) General formula (1) R ¹ _mm M (OR ² ) _n ··· (1) (wherein, M is a metal atom, and R ¹ is the same or different. , An organic group having 1 to 8 carbon atoms, R ² is the same or different,
An alkyl group of from 5 to 5 or an acyl group or phenyl group of from 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M) Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate At least one selected from the group consisting of a decomposition product and a condensate of the metal acylate 2. The organic electroluminescent device according to claim 1, wherein the coating composition further contains a nitrogen-containing organic solvent. 3. The organic electroluminescent device according to claim 1, wherein the coating composition further comprises (c) inorganic fine particles. 4. A gas barrier film wherein a coating film formed from the coating composition containing the component (a) and the component (b) according to claim 1 is laminated on a synthetic resin film. Item 2. An organic electroluminescent device according to Item 1. 5. A gas barrier film is formed on a synthetic resin film from a vapor-deposited layer of a metal and / or an inorganic compound and a coating composition containing the components (a) and (b) according to claim 1. The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device and the coating layer are laminated. 6. The gas barrier film has a thickness of 10 nm to 10 nm.
The organic electroluminescent device according to any one of claims 1 to 5, wherein the thickness is μm. 7. The organic electroluminescent device according to claim 4, wherein the gas barrier film is formed on an outer surface of the resin layer via an adhesive layer. 8. A light-emitting portion having an anode, an organic light-emitting layer, and a cathode is formed on an insulating substrate, and the light-emitting portion is covered with an outside air shielding plate, and the light-emitting portion is provided in a gap between the insulating substrate and the outside air shielding plate. Form a resin layer to surround and seal the light emitting part,
In addition, a method for producing an organic electroluminescent device, comprising forming a gas barrier film comprising a coating composition containing the following components (a) and (b) on the outer surface of a resin layer. (A) Ethylene / vinyl alcohol copolymer (b) General formula (1) R ¹ _mm M (OR ² ) _n ··· (1) (wherein, M is a metal atom, and R ¹ is the same or different. , An organic group having 1 to 8 carbon atoms, R ² is the same or different,
An alkyl group of from 5 to 5 or an acyl group or phenyl group of from 1 to 6 carbon atoms, m and n are each an integer of 0 or more, and m + n is a valence of M) Hydrolyzate of the metal alcoholate, condensate of the metal alcoholate, chelate compound of the metal alcoholate, hydrolyzate of the metal chelate compound, condensate of the metal chelate compound, metal acylate, hydrolysis of the metal acylate At least one selected from the group consisting of a decomposition product and a condensate of the metal acylate