KR20170007415A - Sealed laminate and organic electronic device - Google Patents

Abstract

Provided are a sealing laminate and an organic electronic device which can stably prevent intrusion of moisture for a long period of time and which can stably protect an organic electronic device for a long period of time to prevent the device from deteriorating. A gas barrier member having gas barrier properties, a diffusion layer laminated on the gas barrier member, and a sealing layer laminated on the diffusion layer, wherein the vapor permeability of the diffusion layer is 5 times or more of the vapor permeability of the sealing layer.

Description

[0001] SEALED LAMINATE AND ORGANIC ELECTRONIC DEVICE [0002]

The present invention relates to a sealing laminate and an organic electronic device using the sealing laminate.

BACKGROUND ART An organic EL device (OEL device) using an organic EL (Electro Luminescence) material is used for a display, a lighting device, and the like.

The organic EL material used in this organic EL device is very weak in moisture. Thus, in the conventional organic EL device, in order to prevent intrusion of moisture from the outside, sealing using glass frit or sealing forming a barrier film of several layers directly on the organic EL element is performed. Further, in order to simplify the sealing process, a method of sealing the organic EL element using a glass can or a metal can, a dam-fill type sealing using a curing type adhesive, or a gas barrier film having a barrier layer for flexibility Sealing and the like have been proposed.

Further, in addition to such sealing, it has also been attempted to improve the sealing performance by capturing water intruding by using a desiccant.

For example, Patent Document 1 discloses that a space is formed in a film-shaped sealing member so as to have a concave shape, and a desiccant is disposed in this space in which the organic EL material is sealed, thereby capturing the intruding moisture.

Patent Document 2 discloses a semiconductor device which includes a workpiece to be sealed, a moisture absorption layer provided on the body to be sealed, a resin layer provided on the moisture absorption layer, and an inorganic film which is a barrier film covering these layers, And the moisture is absorbed by the moisture absorption layer.

Patent Document 1: JP-A-2001-118674 Patent Document 2: JP-A-2007-141685

However, in fill-type sealing such as sealing of a dam-fill type in which a curable adhesive is filled and sealing in which a barrier member such as metal, glass or gas barrier film is bonded by an adhesive, Sufficient protection can not be performed, and practical use is not proceeding.

Even when a barrier member having sufficient barrier properties such as metal and glass is sealed with an adhesive, moisture enters from the end face of the adhesive, so that deterioration of the organic EL material occurs early.

Here, it is conceivable to arrange a desiccant in the sealed space and capture the intruding moisture to improve the sealing performance. However, when a barrier member such as a metal, a glass, or a gas barrier film is sealed with an adhesive, since moisture enters from the end face of the adhesive, only the desiccant near the end face absorbs moisture, There is a problem that the device can not be sufficiently protected.

It is conceivable to increase the distance from the end face of the adhesive to the organic EL material in order to suppress the penetration of moisture from the end face. However, there is a demand for an organic EL device used as a display, in particular, a mobile organic EL device such as a cellular phone, to have a smaller edge portion and a larger screen ratio with respect to the size of the product. As a result, it is difficult to increase the distance from the end portion to the organic EL material.

Also, in a structure in which a barrier film is formed directly on an organic EL device or in a structure in which a gas barrier film having a barrier layer is used, moisture may invade from defects in the barrier film and the barrier layer. Therefore, even when a drying agent is disposed between the barrier film or the gas barrier film and the organic EL device, only the drying agent in the vicinity of the defect absorbs moisture, and the organic EL device can not sufficiently protect the organic EL device.

Here, in the case of directly forming the barrier film, it is conceivable to increase the thickness of the barrier layer to prevent the occurrence of defects. However, since it is necessary to form a barrier film at a low temperature so as not to damage the organic EL material, forming a thick inorganic film in order to exhibit sufficient barrier property is very inferior in productivity and leads to an increase in cost.

It is an object of the present invention to solve such a problem of the prior art and to provide a sealing laminate capable of stably preventing intrusion of water for a long period of time and stably protecting the organic electronic element for a long period of time, And an organic electronic device.

The inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, it is possible to stably prevent water intrusion for a long period of time by disposing a diffusion layer between the gas barrier member and the sealing layer, the diffusion layer having a vapor permeability of 5 times or more of the sealing layer , And that the organic electronic device can be stably protected for a long period of time to prevent the device from deteriorating, thereby completing the present invention.

That is, the present invention provides a sealing laminate and an organic electronic device having the following constitutions.

(1) A gas barrier member having gas barrier properties,

A diffusion layer laminated on the gas barrier member,

And a sealing layer laminated on the diffusion layer,

Wherein the water vapor permeability of the diffusion layer is 5 times or more of the water vapor permeability of the sealing layer.

(2) The sealing laminate described in (1), wherein the sealing layer has adhesiveness.

(3) The sealing laminate according to (1) or (2), which has at least a section sealing member covering the end surface of the sealing layer.

(4) The sealed laminate according to (1) or (2), wherein the diffusion layer is formed to cover the end face of the sealing layer.

(5) The sealing laminate described in (4), which has at least a section sealing member covering the end face of the diffusion layer.

(6) The sealed laminate according to any one of (1) to (5), wherein the sealing layer is made of a curable resin.

(7) The sealed laminate according to any one of (1) to (6), wherein the sealing layer has hygroscopicity.

(8) The sealed laminate according to any one of (1) to (7), wherein the diffusion layer is composed of at least one selected from the group consisting of dimethyl siloxane, triacetyl cellulose and acrylic resin.

(9) The sealing laminate according to any one of (1) to (8), wherein the gas barrier member is a gas barrier film having at least a gas barrier support and an inorganic layer composed of a resin film or glass.

(10) The sealed laminate according to any one of (1) to (9), wherein the gas barrier member has a vapor permeability of 1 × 10 ^-4 [g / (m ² · day)] or less.

(11) The sealed laminate according to any one of (1) to (10), wherein the area of the main surface of the sealing layer is 100 mm ² or more, and the total thickness of the sealing layer and the diffusion layer is 50 占 퐉 or less.

(12) A laminate as described in any one of (1) to (11)

An organic electronic element,

And an element substrate in this order.

(13) The organic electronic device according to (12), wherein the organic electronic device is an organic electroluminescent device having a reflective electrode, an organic electroluminescent layer, and a transparent electrode in this order.

(14) The organic electroluminescent device described in (13), wherein the reflective electrode is disposed on the element substrate side, and the transparent electrode is disposed on the sealing laminate side.

According to the present invention, it is possible to provide a sealing laminate and an organic electronic device capable of stably preventing intrusion of water for a long period of time and stably protecting the organic electronic device for a long period of time to prevent the device from deteriorating.

1 is a cross-sectional view conceptually showing an example of an organic electronic device having a sealing laminate of the present invention.
2 is a schematic cross-sectional view showing an enlarged part of the organic electronic device shown in Fig.
3 is a partially enlarged cross-sectional view conceptually showing an example of a gas barrier film.
4 (A) and 4 (B) are schematic cross-sectional views for explaining the operation of the organic electronic device shown in Fig.
5 is a schematic cross-sectional view for explaining the operation of the organic electronic device shown in Fig.
6 (A) and 6 (B) are cross-sectional views conceptually showing an organic electronic device having another example of the sealing laminate of the present invention.
7 (A) to 7 (D) are schematic views for explaining a method of forming an organic electronic device in the embodiment.
8 (A) to 8 (D) are schematic cross-sectional views for explaining sealing in a conventional organic electronic device.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the sealing laminate and organic electronic device of the present invention will be described in detail with reference to the preferred embodiments shown in the accompanying drawings.

Fig. 1 conceptually shows an example of the organic electronic device of the present invention, which is obtained by laminating the sealing laminate of the present invention on an organic electronic laminate.

The organic electronic device 50 shown in Fig. 1 comprises a sealing laminate 10 in which a gas barrier member 20, a diffusion layer 22 and a sealing layer 24 are laminated in order, And an organic electronic laminate 12 on which electronic elements 32 are formed.

1, the organic electronic device 50 has a structure in which the sealing layer 24 side of the sealing laminate 10 and the organic electronic device 32 side of the organic electronic laminate 12 are stacked facing each other Respectively.

The sealing laminate 10 is laminated on the organic electronic element 32 and the organic electronic element 32 is sealed to prevent the organic electronic element 32 from being deteriorated by moisture.

Here, the sealing laminate 10 of the present invention has a structure in which the diffusion layer 22 is laminated on the sealing layer 24. By providing the diffusion layer 22, it is possible to prevent the intrusion of water vapor concentrated on a part of the end face or the like of the sealing laminate 10 and to concentrate only on a part of the sealing layer 24, It can be stably protected for a long period of time to prevent deterioration.

This point will be described in detail later.

In the organic electronic device 50 of the present invention, the organic electronic laminate 12 is a well-known organic EL device having, for example, an organic electronic device 32 as a light emitting device using an organic EL material.

Further, the organic electronic laminate 12 used in the present invention is not limited to the organic EL device, and various known devices having organic electronic devices such as organic solar cells can be used.

In the following description, an example using an organic EL device as the organic electronic laminate 12 is described.

In the organic EL device as the organic electronic laminate 12, the element substrate 30 can be used as an element substrate used in various organic EL devices. Specifically, an element substrate made of glass, plastic, metal, ceramic, or the like is exemplified.

Here, in the organic electronic device 50 of the present invention, in order to prevent deterioration of the organic electronic device 32 due to moisture or the like, moisture or the like, which penetrates the device substrate 30 and reaches the organic electronic device 32 It is desirable to be able to prevent such a problem. Therefore, it is preferable to use a substrate made of a material such as glass or metal having a low content of moisture or the like and a low transmittance such as moisture. Alternatively, the gas barrier film used as the gas barrier member 20 of the sealing laminate 10 described later can be suitably used as the element substrate 30 in view of the low transmittance of water or the like.

Here, in the organic electronic device 50 of the present invention, when a gas barrier film or a glass plate described later is used as the gas barrier member 20 of the sealing laminate 10 sealing the organic electronic laminate 12, It can be used as a top emission type organic electronic device 50 that emits light from the side opposite to the element substrate 30, that is, from the sealing laminate 10 side.

When the organic electronic device 50 is a top emission type, the element substrate 30 need not have optical transparency. Therefore, when the organic electronic device 50 of the present invention is used as a top emission type, an aluminum foil having an anodic oxide film on its surface or a laminate of an aluminum foil and a polyimide, May be used. At this time, by using a gas barrier film as the gas barrier member 20, a flexible organic electronic device 50 can be obtained.

On the other hand, by using a light-transmissive material such as glass or a gas barrier film as the element substrate 30, it can be used as a bottom emission type organic electronic device 50 that emits light from the element substrate 30 side.

Alternatively, the gas barrier member 20 and the element substrate 30 may be configured to emit light from both surfaces using a light-permeable material such as glass or a gas barrier film.

On the element substrate 30, an organic EL element which is an organic electronic element 32 is formed.

2 is a schematic cross-sectional view showing an enlarged part of the organic electronic device 50. As shown in Fig.

2, the organic electronic device 32 has a known structure having an organic electroluminescent layer 40 and a transparent electrode 42 and a reflective electrode 44 serving as an electrode pair sandwiching the organic electroluminescent layer 40 Organic EL device.

Here, the organic electronic device 50 shown in Fig. 2 is a top emission type. Therefore, the transparent electrode 42 is disposed on the side of the sealing laminate 10, and the reflective electrode 44 is disposed on the side of the element substrate 30.

The organic electroluminescent layer 40 may be any layer having a known layer structure including a light emitting layer made of an organic EL material, a hole injecting layer, a hole transporting layer, an electron transporting layer, an electron injecting layer and the like.

As the transparent electrode 42, various known electrodes having light transmittance that transmit light emitted from the organic electroluminescent layer 40, such as a conductive metal oxide such as indium tin oxide (ITO), can be used .

As the reflective electrode 44, various known electrodes used as electrodes of organic EL elements can be used.

The organic electroluminescent layer 40, the transparent electrode 42 and the reflective electrode 44 may be formed by a known method depending on the use and size of the organic electronic device 50. [

In the organic electronic device 50 shown in Fig. 2, the organic electronic laminate 12 is composed of the element substrate 30 and the organic electronic element 32 formed on the element substrate 30 , But the present invention is not limited thereto, and may have a protective film covering the organic electronic element 32 or the like.

As the protective film, various films (layers) made of a material exhibiting gas barrier properties, which are used in a known organic EL device, can be used. Specifically, a film made of an inorganic compound having gas barrier properties is exemplified, and among these, a film made of a silicon compound such as silicon nitride, silicon oxide, and silicon oxynitride is suitably exemplified.

Next, the sealing laminate 10 will be described.

The sealing laminate 10 seals an organic electronic element 32 such as an organic EL element to protect the organic electronic element 32 from moisture.

1, the sealing laminate 10 has a structure in which a gas barrier member 20, a diffusion layer 22, and a sealing layer 24 are laminated in this order.

The sealing laminate 10 shown in Fig. 1 is constructed by laminating three layers of the gas barrier member 20, the diffusion layer 22 and the sealing layer 24, but the sealing laminate 10 of the present invention is not limited thereto, Is not limited to this, and may have another layer. For example, a light extraction layer, a refractive index adjustment layer, or the like.

The gas barrier member 20 is a member having gas barrier properties. The gas barrier member 20 is a member that is large enough to cover the entire organic electronic element 32 and is a member that restrains water from reaching the organic electronic element 32 mainly from the outside.

The gas barrier member 20 is not particularly limited as long as it has a gas barrier property that can protect the organic electronic device 32, and examples thereof include a glass plate, a metal plate, and a gas barrier film. Among them, a glass plate and a gas barrier film having light transmittance which can be used as a top emission type organic electronic device 50 are suitably exemplified. Further, a gas barrier film is more suitably exemplified from the viewpoint of flexibility.

It is preferable that the gas barrier member 20 has a vapor permeability of 1 × 10 ^-4 [g / (m ² · day)] or less.

In the case of sealing the organic electronic laminate 12 using the sealing laminate 10 having the gas barrier member 20 having a low water vapor permeability, that is, a high gas barrier property, the cross section of the sealing laminate 10 Or the penetration of water vapor from a local portion such as a defect in the gas barrier member becomes relatively large.

Therefore, the present invention which can more appropriately prevent entry of water vapor from a cross section of the sealing laminate 10 or from a local portion such as a defect of the gas barrier member, has a gas barrier member 20 having a high gas barrier property It is more suitably applicable when the sealing laminate 10 is used.

As the gas barrier film used as the gas barrier member 20, those having at least one inorganic layer on the gas barrier support are suitably used.

For example, as shown in Fig. 3, the gas barrier film 20a has an organic layer 27 on the gas barrier support 26, and has an inorganic layer 28 on the organic layer 27. [

The gas barrier film 20a has at least one combination of the inorganic layer 28 and the organic layer 27 serving as a base of the inorganic layer 28 on the gas barrier support 26 desirable. Therefore, the gas barrier film 20a may have two, or three or more, combinations of the inorganic layer 28 and the underlying organic layer 27. [

The organic layer 27 serves as a base layer for appropriately forming the inorganic layer 28. The larger the number of laminated layers of the organic layer 27 and the inorganic layer 28 is, A barrier film can be obtained.

It is preferable that the gas barrier film 20a has the outermost surface of the inorganic layer 28 and it is preferable that the diffusion layer 22 is laminated on the surface of the inorganic layer 28 side.

The outermost gas is shielded by the inorganic layer 28 even if outgas is emitted from the gas barrier support 26 or the organic layer 27 by making the outermost surface of the gas barrier film 20a an inorganic layer 28, The sealing layer 24 and the organic electronic element 32 can be prevented from reaching the sealing layer 24 and the organic electronic element 32.

The gas barrier support 26 of the gas barrier film 20a may be variously used as a support in a known gas barrier film.

Among them, a film made of various plastics (high molecular material / resin material) is suitably used because it is easy to make thin and lightweight and is suitable for making the organic electronic device 50 flexible.

Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, transparent polyimide, A plastic film made of at least one material selected from the group consisting of latex, polymethacrylate, cycloolefin polymer (alicyclic polyolefin), cycloolefin copolymer, and triacetyl cellulose is suitably exemplified.

The thickness of the support for gas barrier 26 may be appropriately set depending on the use and size of the organic electronic device 50. [ Here, according to the study by the present inventors, it is preferable that the thickness of the gas barrier support 26 is about 10 m to 200 m. When the thickness of the support for gas barrier 26 is set in this range, preferable results are obtained in terms of weight reduction and thinning of the organic electronic device 50. [

The gas barrier support 26 may be provided with functions such as antireflection, retardation control, and light extraction efficiency on the surface of such a plastic film.

The organic layer 27 serves as a base layer of the inorganic layer 28 mainly exhibiting gas barrier properties in the gas barrier film 20a.

The organic layer 27 can be variously used as the organic layer 27 in a known gas barrier film. For example, the organic layer 27 is a film composed mainly of an organic compound, and basically, a material formed by crosslinking a monomer and / or an oligomer can be used.

The gas barrier film 20a has the underlying organic layer 27 so that the organic layer 27 also functions as a cushion of the inorganic layer 28. [ This allows the cushioning effect of the organic layer 27 when the organic electronic device 50 is pressed when the organic electronic layered product 12 and the sealing laminate 10 are adhered to each other, , It is possible to prevent the inorganic layer 28 from being damaged.

As a result, in the organic electronic device 50, the gas barrier film 20a exhibits adequate gas barrier performance, and deterioration of the organic electronic device 32 due to moisture can be suitably prevented.

The gas barrier film 20a has an organic layer 27 serving as a base of the inorganic layer 28 so that unevenness on the surface of the gas barrier support 26 and foreign matter The inorganic layer 28 can be formed to have a suitable film-forming surface. As a result, it is possible to form an appropriate inorganic layer 28 on the entire surface of the film formation surface without any gap and without cracks or gold. As a result, a high gas barrier performance such that the water vapor transmission rate becomes 1 × 10 ^-4 [g / (m ² · day)] or less can be obtained.

As the material for forming the organic layer 27 in the gas barrier film 20a, various organic compounds (resin / polymer compound) can be used.

Specific examples of the resin include polyolefins such as polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acyl But are not limited to, polyolefins, polyurethanes, polyurethanes, polyurethanes, polyetherketones, polycarbonates, alicyclic polyolefins, polyarylates, polyethersulfones, polysulfones, fluorene ring-modified polycarbonates, alicyclic modified polycarbonates, Ester or acryloyl compound, or a film of polysiloxane or other organic silicon compound is suitably exemplified. These may be used in combination.

Among them, an organic layer 27 composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group in a functional group is suitable from the viewpoint of excellent glass transition temperature and strength.

Among them, in view of low refractive index, high transparency, and excellent optical properties, in addition to the above strength, it is preferable to use a polymer of a monomer or oligomer of acrylate and / or methacrylate as a main component and a glass transition temperature of 120 C or more is suitably exemplified as the organic layer 27. [

Among them, particularly preferred are dipropylene glycol di (meth) acrylate (DPGDA), trimethylol propane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) Acrylic resins or methacrylic resins having a bifunctional or higher molecular weight, particularly a trifunctional or higher acrylate and / or methacrylate monomer or oligomer polymer as a main component are suitably exemplified. It is also preferable to use a plurality of these acrylic resins or methacrylic resins.

Since the inorganic layer 28 can be formed on the base having a rigid skeleton by forming the organic layer 27 with acrylic resin or methacrylic resin, the inorganic layer 28 having a higher density and higher gas barrier property can be formed can do.

The thickness of the organic layer 27 is preferably 0.5 占 퐉 to 5 占 퐉.

By setting the thickness of the organic layer 27 to 0.5 m or more, the effect as a cushion at the time of bonding the organic electronic laminate 12 and the sealing laminate 10 is sufficiently exhibited, Can be more reliably prevented from being damaged. When the thickness of the organic layer 27 is 1 占 퐉 or more, it is preferable to appropriately form the inorganic layer 28 so that the inorganic layer 28 having no cracks or cracks is formed on the entire surface of the deposition surface It is possible to form a film on the film.

When the thickness of the organic layer 27 is 5 占 퐉 or less, problems such as cracks in the organic layer 27 and curling of the gas barrier film 20a, which are caused by the organic layer 27 being too thick, .

Considering the above points, the thickness of the organic layer 27 is more preferably 1 占 퐉 to 5 占 퐉.

When the gas barrier film has a plurality of organic layers 27, the thicknesses of the respective organic layers 27 may be the same or different from each other.

In the case of having a plurality of organic layers 27, the forming materials of the respective organic layers 27 may be the same or different. However, in terms of productivity and the like, it is preferable to form all the organic layers 27 from the same material.

The organic layer 27 may be formed by a known method such as a coating method or a flash evaporation method.

It is preferable that the organic layer 27 contains a silane coupling agent in order to improve the adhesion with the inorganic layer 28 which is a lower layer of the organic layer 27. [

On the organic layer 27, the inorganic layer 28 is formed by using the organic layer 27 as a base.

The inorganic layer 28 is a film containing an inorganic compound as a main component and mainly exhibits gas barrier properties in the gas barrier film 20a.

As the inorganic layer 28, various membranes made of an inorganic compound exhibiting gas barrier properties can be used.

Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); Metal nitrides such as aluminum nitride; Metal carbides such as aluminum carbide; Silicon oxides such as silicon oxide, silicon oxynitride, silicon oxycarbide, and silicon oxynitride; Silicon nitrides such as silicon nitride and silicon carbide; Silicon carbide such as silicon carbide; Their hydrides; Mixtures of two or more thereof; And a hydrogen-containing water and a film made of an inorganic compound are suitably exemplified.

In particular, a film composed of a silicon compound such as silicon oxide, silicon nitride, silicon oxynitride and silicon oxide is suitably exemplified from the viewpoint of high transparency and excellent gas barrier properties. Particularly, a film made of silicon nitride has a higher transparency in addition to better gas barrier properties and is suitably exemplified.

When the gas barrier film has a plurality of inorganic layers 28, the materials for forming the inorganic layers 28 may be different from each other. However, considering productivity and the like, it is preferable to form all the inorganic layers 28 from the same material.

The thickness of the inorganic layer 28 may be appropriately determined depending on the forming material so that the desired gas barrier properties can be exhibited. Further, according to the study of the present inventors, it is preferable that the inorganic layer 28 has a thickness of 10 to 200 nm.

By setting the thickness of the inorganic layer 28 to 10 nm or more, it is possible to form the inorganic layer 28 stably expressing sufficient gas barrier performance. If the thickness of the inorganic layer 28 is generally 200 nm or less, it is possible to prevent the occurrence of cracks .

In consideration of this, the thickness of the inorganic layer 28 is preferably 10 nm to 100 nm, and more preferably 15 nm to 75 nm.

When the gas barrier film has a plurality of inorganic layers 28, the inorganic layers 28 may have the same thickness or different thicknesses.

The inorganic layer 28 may be formed by a known method depending on the forming material. Specifically, a vapor deposition method such as plasma CVD such as CCP (Capacitance-coupled Plasma) -CVD (Chemical Vapor Deposition) or ICP (Inductively Coupled Plasma) -CVD, sputtering such as magnetron sputtering or reactive sputtering, .

As described above, in the sealing laminate 10 of the present invention, the diffusion layer 22 is laminated on the gas barrier member 20, and the sealing layer 24 is laminated on the diffusion layer 22.

First, the sealing layer 24 will be described.

The sealing layer 24 is a portion formed on the outermost surface side of the sealing laminate 10 and has adhesiveness so that the adhesive layer when the sealing laminate 10 is laminated on the organic electronic laminate 12 . At this time, the sealing layer 24 is adhered to fill the irregularities on the surface of the organic electronic laminate 12.

Here, the sealing layer 24 preferably has hygroscopicity. Specifically, the hygroscopicity of the sealing layer 24 is preferably 1 wt% to 10 wt%, more preferably 1 wt% to 5 wt%.

The sealing layer 24 is provided with hygroscopicity to absorb water penetrating from the end face of the sealing laminate 10 or from defects of the gas barrier member 20 and the like, . Here, in the present invention, since the diffusion layer 22 is provided between the sealing layer 24 and the gas barrier member 20, the intruding moisture is diffused in the diffusion layer 22, so that the entirety of the sealing layer 24 Can be used to absorb moisture. Therefore, only a part of the sealing layer 24 absorbs moisture and is prevented from prematurely deactivating, so that the organic electronic element 32 can be stably protected for a long period of time.

This point will be described in detail later.

Here, in the sealing laminate 10 of the present invention, the ratio of the water vapor permeability of the sealing layer 24 to the water vapor permeability of the diffusion layer 22 to be described later is at least 5 times. Thus, the water vapor permeability of the sealing layer 24 is low, the more preferable, and water vapor transmission (WVTR) is, 0.1 ~ 100 [g / ( m 2 · day)] , and is preferably of, 0.1 ~ 10 [g / ( m 2 Day)] is more preferable.

In the present invention, the water vapor transmission rate (WVTR) is a value measured based on the moisture permeability test method (cup method) of the moisture-proof packaging material of JIS Z0208.

The thickness of the sealing layer 24 is not particularly limited, but is preferably 5 to 100 占 퐉 from the viewpoints of adhesiveness, hygroscopicity, trackability to the unevenness of the surface of the organic electronic laminate 12, and the like.

As a material for forming the sealing layer 24, a material which can adhere the organic electronic laminate 12 and the sealing laminate 10 with a sufficient adhesion force may be appropriately selected.

Specifically, as the sealing layer 24, an adhesive sheet such as an OCA (Optically Clear Adhesive) sheet may be used, or an organic layer in which the resin is cured by polymerization, heat, or the like may be used.

Examples of the curable resin include a silicone resin, an acrylic resin, a methacrylic resin, an epoxy resin, a melamine resin, a polyester resin, a urethane resin, an epoxy acrylate resin and a cyclic olefin resin. Among them, an acrylic resin, an epoxy resin, an epoxy acrylate resin, and a cyclic olefin resin are preferable. It is also preferable to use a resin comprising at least three polyfunctional acrylate / methacrylate compounds.

Further, a resin for adjusting the viscosity and curability may be mixed with these curable resins as main components. For example, a styrene-butadiene block copolymer may be included for viscosity adjustment.

These curable resins may be used alone, or two or more of them may be used in combination.

The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule. Specific examples thereof include bisphenol epoxy resins such as polybutadiene epoxy resins, bisphenol A epoxy resins and bisphenol F epoxy resins, naphthalene epoxy resins, aliphatic epoxy resins, biphenyl epoxy resins, glycidyl Amine-type epoxy resins, and hydrogenated bisphenol A-type epoxy resins; epoxy-modified epoxy resins such as epoxy-modified silicone, phenol novolac epoxy resin and cresol novolak epoxy resin; alicyclic epoxy resins; Halogenated epoxy resins such as glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and brominated epoxy resins, rubber-modified epoxy resins, and oil-modified epoxy resins. Modified epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymer, epoxy Group-containing may be mentioned polyester resin, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resin and the like. Among them, a bisphenol A type epoxy resin, a naphthalene type epoxy resin, and an alicyclic epoxy resin can be exemplified from the viewpoint that the photopolymerization property is higher and the photocuring proceeds more efficiently even with a smaller amount of light. These epoxy resins may be used alone, or two or more of them may be used in combination.

Among the above-mentioned epoxy resins, it is preferable to use a bifunctional epoxy resin from the viewpoint that the curing shrinkage stress is small and the adhesion of the cured product is high. From the viewpoint of low moisture permeability and hygroscopicity, it is preferable to use polyurethane resin or polyurethane resin.

As the acrylic resin, a resin obtained by mixing a modified acrylate as a base resin and an acrylate monomer as a reactive diluent for viscosity adjustment can be given.

Specifically, it is possible to use a resin having an acrylate-based functional group, for example, a polyester resin having a relatively low molecular weight, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, (Meth) acrylate or the like of a multifunctional compound such as poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, Monofunctional monomers such as benzene, toluene, xylene, naphthalene, xylene, naphthylene, xylene, xylene, Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Acrylic acid, methacrylic acid, itaconic acid, maleic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, lauryl methacrylate T-butyl acrylate, lauryl acrylate, stearyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate, cyclohexyl acrylate, Butylaminoethyl methacrylate, 2-cyanoethyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-ethoxyethyl methacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, nonylphenoxypolyethylene glycol acrylate Phenoxy diethylene glycol acrylate, phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, benzyl acrylate, benzyl methacrylate, 2-ethyl Hexyl carbitol acrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, perfluorooctyl ethyl methacrylate, isocyanatoethyl methacrylate, dicyclopentanyl acrylate Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate (Tg = 107 ° C), N (methyl methacrylate) -Methylol methacrylamide, acrylamide, tetrahydrofurfuryl methacrylate, diacetone acrylamide, N-vinylpyrrolidone, isobornyl methacrylate, A mixture of acrylate, isobornyl acrylate, and the like may be mentioned a resin obtained.

In addition, as the photopolymerization initiator in the above-mentioned curable resin, at least one selected from the group consisting of acetophenones, benzophenones, meihyl benzoyl benzoate,? -Amyl oxime ester, tetramethylthiuram monosulfide, Amine, triethylamine, tri-n-butylphosphine, and the like. In particular, it is preferable to mix urethane acrylate as the oligomer and dipentaerythritol hexaacrylate as the monomer.

As the epoxy acrylate, a resin obtained by mixing an acrylate having at least one hydroxyl group and at least two ethylenic double bonds in the molecule, an epoxy resin having at least two glycidyl groups in the molecule, and a thermal radical polymerization initiator . Specific examples include (meth) acrylate monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and methyl glycidyl (meth) acrylate .

Examples of the acrylate having at least one hydroxyl group and at least two ethylenic double bonds in the molecule include bisphenol A type epoxy acrylate, bisphenol F type epoxy acrylate, 1,4-butenediol diglycidyl ether acrylate , 1,6-hexanediol diglycidyl ether acrylate, diethylene glycol diglycidyl ether acrylate, dipropylene glycol diglycidyl diacrylate, ethoxylated isocyanate And at least one acrylate selected from the group consisting of dicarboxylic acid diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, Among them, it is more preferable to include at least one of bisphenol A type epoxy acrylate and bisphenol F type epoxy acrylate.

The curable resin may contain a silane coupling agent or a silane-modified epoxy resin, if necessary. It is also possible to use a silane coupling agent and a silane-modified epoxy resin in combination. By mixing these components in the curable resin as the sealing layer 24, deterioration of the adhesive force due to humidification can be suppressed.

As the coupling agent, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N - β- (N-vinylbenzylaminoethyl) -aminopropyltrimethoxysilane, hexamethylsilazane, and the like; silane coupling agents having an amino group such as? -glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltri A silane coupling agent having an epoxy group such as methoxysilane, a silane coupling agent having a mercapto group such as? -Mercaptopropyltrimethoxysilane, and a halogen group such as? -Chloropropyltrimethoxysilane (2, 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl dimethacryl isostearoyltitanate , Isopropyl diacrylate (Dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl triisodecyl benzene A titanate-based coupling agent such as isopropyl tributyl phenyl titanate, an aluminum-based coupling agent such as acetoalkoxy aluminum diisopropylate, and a zirconium-based coupling agent such as an acetylacetone-zirconium complex, etc. .

Examples of the silane-modified epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, And alkoxysilane is chemically bonded to the hydroxyl group.

The curable resin to be the sealing layer 24 preferably contains an inorganic filler for the purpose of further improving moisture resistance of the cured product.

The inorganic filler is not particularly limited and includes, for example, talc, asbestos, silica, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, Barium, gypsum, calcium silicate, cericite activated clay, and the like.

In order to impart hygroscopicity to the sealing layer 24, a desiccant is preferably contained in the sealing layer 24.

The sealing layer 24 contains a desiccant to absorb the water penetrating from the end face of the sealing laminate 10 or from defects of the gas barrier member 20 or the like so that deterioration due to moisture of the organic electronic element 32 .

The drying agent may be an organic metal complex or an inorganic drying agent.

The organometallic complex is preferably an organometallic compound having a structure represented by the formula (1), more preferably a structure represented by - [M (OR) -O] n-, particularly preferably a cyclic AlO- An organometallic compound of a trivalent metal having a ring structure of at least two, and a trivalent metal of aluminum is preferable.

Herein, R ₁ , R ₂ and R ₃ in the general formula (1) represent hydrogen, an alkyl group having at least 1 carbon atom, an aryl group, a cycloalkyl group or a heterocyclic group. It is also possible to substitute a part of hydrogen of each group with a halogen group. R ₁ , R ₂ , and R ₃ may have different contributions, have the same contribution, and may be connected to each other. Alternatively, it may be a polymer.

[Chemical Formula 1]

Specific examples thereof include aluminum oxide 2-ethylhexanoate (OLF AOO from Hoffse- yaku Kabushiki Kaisha), aluminum oxide isopropylate (Algermer 7 from Kawaken Fine Chemical Co.), aluminum oxide stearate (Olef AOS manufactured by Hoffesayaku K.K.), aluminum oxide ethylate, and the like.

In addition, non-cyclic aluminum-triisopropoxide (AIP) is also preferred.

Also, the water absorbent described in Japanese Laid-Open Patent Publication No. 2005-298598 and the drying system described in Japanese Laid-Open Patent Publication No. 2006-297380 can be used.

Examples of the inorganic drying agent include alkaline earth metal oxides such as calcium oxide (CaO), barium oxide (BaO), and magnesium oxide (MgO); Lithium sulfate (Li ₂ SO _4), sodium sulfate (Na ₂ SO _4), calcium sulfate (CaSO _4), magnesium sulfate (MgSO _4), cobalt sulfate (CoSO _4), sulfate, gallium _{(Ga 2 (SO 4) 3} ) sulfate, titanium _{(Ti (SO 4) 2)} , nickel sulfate (NiSO ₄₎ sulfate, calcium chloride, such as (CaCl _2), phosphorus pentoxide (P ₂ O _5), potassium hydroxide (KOH), sodium hydroxide (NaOH), Potassium bromate (KBr), calcium bromide (CaBr ₂ ), copper sulfate (CuSO ₄ ), zinc chloride (ZnCl ₂ ), zeolite, silica gel and activated alumina.

In the case of using an inorganic drying agent, it is preferable to reduce the particle size in consideration of the haze value and the transparency of the sealing layer 24, and preferably 10 nm or less.

The content of the desiccant in the sealing layer 24 may be appropriately set depending on the type of the desiccant and the required performance. Specifically, it is preferably from 10 to 80 mass%, more preferably from 30 to 70 mass%, and particularly preferably from 40 to 60 mass%.

It is preferable that the sealing layer 24 has transparency. Specifically, the sealing layer 24 preferably has a light transmittance of visible light (wavelength 400 to 800 nm) of 90% or more, and preferably a haze value of 0.5% or less.

The sealing layer 24 is preferably formed on the diffusion layer 22 of the gas barrier member 20 by coating. Therefore, it is preferable to prepare a coating composition by mixing a material for forming the sealing layer 24 and a solvent.

The SP value (solubility parameter) of the solvent is preferably from 8 to 13, and the difference in SP value from the curable resin selected as the binder is preferably within ± 2 from the viewpoint of obtaining a flat transparent sealing layer 24 Do. Specifically, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate and the like are preferable as the solvent.

There is no particular limitation on the coating method for forming the sealing layer 24, but when a gas barrier film is used as the gas barrier member 20, since it is difficult to destroy the inorganic layer of the gas barrier film, .

In the case of forming the sealing layer 24 on a long gas barrier film, the sealing layer 24 is formed by applying and curing the coating composition while transporting the long gas barrier film in the longitudinal direction, And may be formed by roll-to-roll.

Next, the diffusion layer 22 will be described.

The diffusion layer 22 is a region which is laminated between the gas barrier member 20 and the sealing layer 24 and has a diffusion property of water vapor.

In the sealing laminate (10) of the present invention, the water vapor permeability of the diffusion layer (22) is 5 times or more and preferably 8 times or more of the water vapor permeability of the sealing layer (24).

Specifically, the water vapor transmission rate (WVTR) of the diffusion layer 22 is preferably 10 to 1000 g / (m ² · day).

Here, a schematic sectional view of an example of a conventional organic electronic device is shown in Fig. 8 (A). 8 (B) to 8 (D) are schematic diagrams for explaining the penetration of moisture in the organic electronic device shown in Fig. 8 (A). 8 (B) to 8 (D), the direction of entry of water is indicated by an arrow, and the area in which moisture enters is represented by the dot of the dot.

8A, a conventional organic electronic device 200 has a structure in which a gas barrier member 208 such as a metal plate or a glass plate is bonded to an organic electronic device (not shown) on the element substrate 202 via an adhesive layer 206 204 so as to seal the organic electronic device 204.

As described above, in such a conventional organic electronic device 200, moisture penetrates from the end face of the adhesive layer 206, as indicated by the arrow in Fig. 8 (B). Here, in the case where the adhesive layer 206 has hygroscopicity, the moisture penetrated from the end face is absorbed in the region near the end face of the adhesive layer 206, that is, in the region indicated by the dot of the dot in the figure, Thereby preventing it from reaching the device 204.

However, since moisture penetrates from the end face, only the region near the end face of the adhesive layer 206 absorbs water and is inactivated. That is, in the conventional organic electronic device 200, only the area from the end face to the end portion of the organic electronic device 204 can effectively utilize the moisture absorption function of the adhesive layer 206. Therefore, as shown in Fig. 8 (C), if the region between the end face of the adhesive layer 206 and the organic electronic element 204 is deactivated according to the elapse of time, although the region exhibiting no moisture absorption function is present , Moisture reaches the organic electronic element 204. Therefore, in the conventional organic electronic device 200, invasion of moisture can not be stably prevented for a long period of time.

In addition, when the gas barrier member 208 has a defect, moisture enters from the defect. Even in such a case, as shown in Fig. 8 (D), even though only the adhesive layer 206 around the defect absorbs moisture and is inactivated to have moisture absorptive function, .

In Fig. 8 (D), for the sake of explanation, only the inactivated state due to moisture invading from the defect is shown.

On the other hand, in the organic electronic device 50 in which the organic electronic laminate 12 is sealed using the sealing laminate 10 of the present invention, the sealing laminate 10 is sealed with the gas barrier member 20, And a diffusion layer (22) between the layers (24).

Intrusion of moisture in the organic electronic device 50 shown in Fig. 1 will be described with reference to Figs. 4 (A), 4 (B) and 5. 4 (A), 4 (B), and 5, the direction of intrusion of moisture is indicated by an arrow, and the area in which water enters is represented by the dot of the dot.

Since the diffusion layer 22 is provided between the gas barrier member 20 and the sealing layer 24 when moisture enters from the end face of the sealing laminate 10 in the organic electronic device 50, The moisture is absorbed in the end surface of the sealing layer 24 and the moisture permeates the inside of the diffusion layer 22 to be absorbed into the sealing layer 24 from the surface on the diffusion layer 22 side . That is, as shown by dotted dots in the figure, the sealing layer 24 absorbs moisture in the region near the end face and the region on the diffusion layer 22 side.

4 (B), even if the sealing layer 24 is inactivated, the area from the end face of the sealing layer to the end of the organic electronic element 32 and the area on the side of the diffusion layer 22 The entire area from the surface to the surface of the organic electronic device 32, that is, the entirety of the sealing layer 24, can be effectively used to absorb moisture. This lowers the moisture concentration per unit area, slows the diffusion rate of water, slows down the arrival of moisture in the organic electronic element 32, and stably protects the organic electronic element 32 for a long period of time. Thus, the organic electronic device 50 can be made longevity.

Since the diffusion layer 22 is provided between the gas barrier member 20 and the sealing layer 24 even when moisture enters from the defect of the gas barrier member 20, The moisture penetrating from the defect is diffused in the diffusion layer 22 and absorbed into the sealing layer 24 on the entire surface of the diffusion layer 22 side as shown by the dotted dot in the figure.

Therefore, even in the case of moisture penetrating from the defect of the gas barrier member 20, the area from the surface of the sealing layer 24 on the diffusion layer 22 side to the surface of the organic electronic element 32, The whole can be effectively used to absorb moisture. This makes it possible to sufficiently slow moisture to reach the organic electronic element 32 and to stably protect the organic electronic element 32 for a long period of time.

Here, among the gas barrier members 20, since the gas barrier film has a thin and tough inorganic layer as the barrier layer, defects tend to occur. Therefore, in the present invention, when the gas barrier film 20 is used as the gas barrier film 20, moisture can be diffused from the defect of the gas barrier member 20 to suppress deactivation of the sealing layer as described above And the like.

In addition, since the entire sealing layer 24 can be effectively used, even if the moisture absorption performance of the sealing layer 24 is reduced, it can be stably protected for a longer period of time than in the prior art. Therefore, the content of the desiccant can be reduced, and the range of the desiccant can be selected.

In addition, since the whole of the sealing layer 24 can be effectively used, even if the thickness of the sealing layer 24 is made thin, necessary moisture absorption performance can be obtained.

It is preferable that the larger the major surface of the sealing layer 24 is, the larger the difference between the vapor permeability of the sealing layer 24 and the diffusion layer 22 is, in order to use the sealing layer 24 farther from the end face more effectively , For example, 8 times or more.

The thickness of the diffusion layer 22 is not particularly limited and is sufficient if it can sufficiently diffuse the water vapor. From the viewpoints of diffusion of water vapor and suppression of invasion of water vapor, the diffusion layer 22 is preferably 5 to 100 mu m, more preferably 5 to 50 mu m, And particularly preferably from 5 to 20 mu m.

The total thickness of the diffusion layer 22 and the sealing layer 24 is preferably 50 占 퐉 or less and more preferably 20 占 퐉 or less from the viewpoint of reducing the intrusion of moisture from the end face of the sealing laminate 10 itself.

In the sealing laminate 10 of the present invention, since the entire sealing layer 24 can be used by having the diffusion layer 22, the sealing laminate 10 can be used more easily when the area of the main surface of the sealing laminate 10 is large, And can be suitably applied. More specifically, it can be more suitably applied when the total thickness of the diffusion layer 22 and the sealing layer 24 is 50 占 퐉 or less and the area of the main surface of the sealing layer 24 is 100 mm ² or more.

As a material for forming the diffusion layer 22, it may be suitably selected that the water vapor permeability is 5 times or more of the sealing layer 24.

As described above, the water vapor permeability (WVTR) of the diffusion layer 22 is preferably 10 to 1000 g / (m ² · day).

Specific examples of the material that satisfies the range of the water vapor transmission rate include polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE), polyimide (PI), polystyrene (PS), polyethylene oxide Triacetylcellulose (TAC), dimethylpolysiloxane (PDMS), low cost acrylic resin, etc. are preferable. Among them, TAC, PDMS and low cost acrylic resin are preferable in that the water vapor transmission rate is higher.

As the low-cost acrylic resin, a commercially available OCA sheet may be used. For example, 8146-1 to 8146-4 of Sumitomo 3M Limited, MG series of Kagaku Kagaku Kogyo Co., Ltd., and the like.

In addition, any resin or filler may be mixed with these materials as a main component in order to adjust the water vapor transmission rate.

It is preferable that the diffusion layer 22 has transparency. Specifically, the diffusing layer 22 preferably has a light transmittance of visible light (wavelength 400 to 800 nm) of 90% or more, and preferably a haze value of 0.5% or less.

The method of forming the diffusion layer 22 is not particularly limited. For example, the diffusion layer 22 may be formed by applying a coating liquid to be the diffusion layer 22 on the gas barrier member 20.

Here, in the organic electronic device 50 shown in Fig. 1, the sealing laminate 10 is composed of the three layers of the gas barrier member 20, the diffusion layer 22 and the sealing layer 24, The present invention is not limited thereto and may have at least a surface sealing member covering the end surface of the sealing layer 24. [

Fig. 6 (A) shows a schematic sectional view of an organic electronic device using another example of the sealing laminate of the present invention.

The organic electronic device 60 shown in Fig. 6A is different from the organic electronic device 50 (Fig. 6A) except that the sealing laminate 62 having the end surface sealing member 64 is used instead of the sealing laminate 10 The same parts are denoted by the same reference numerals, and different parts are mainly used in the following description.

The organic electronic device 60 shown in Fig. 6A has a structure in which a sealing laminate 62 is laminated on an organic electronic laminate 12 on which an organic electronic device 32 is formed on an element substrate 30 .

The sealing laminate 62 includes a laminate in which the gas barrier member 20, the diffusion layer 22 and the sealing layer 24 are laminated in order, a side surface sealing member 64 disposed so as to cover the end surface of the laminate, .

The end face sealing member 64 is for reducing the penetration of moisture from the end faces of the diffusion layer 22 and the sealing layer 24. [ Therefore, the cross-section sealing member 64 preferably has a low water vapor transmission rate, and more preferably 0.01 to 30 [g / (m ² · day)].

The material for forming the side-surface sealing member 64 is not particularly limited as long as it can reduce the penetration of moisture from the end faces of the diffusion layer 22 and the sealing layer 24. Concretely, for example, NXR5516 manufactured by Nagase Chemical Industry Co., Ltd. and TB3124 manufactured by Sreebont Kabushiki Kaisha are preferred, and an inorganic layer such as polysilazane formed by coating of an inorganic layer Or an inorganic barrier layer formed by vacuum evaporation is also preferable.

The thickness of the end surface sealing member 64, that is, the thickness in the direction perpendicular to the end surface of the sealing layer 24 is not particularly limited, but from the viewpoint of reducing the intrusion of moisture and shortening the length of the frame, The thickness of the inorganic material is preferably 0.1 to 1 占 퐉, and the thickness of the organic material is preferably 10 to 1000 占 퐉.

The method of forming the end surface sealing member 64 is not particularly limited and can be formed by a forming method according to the material for forming the end surface sealing member 64. [ For example, it can be formed by coating, vacuum film formation or the like.

6A, the end surface sealing member 64 is formed so as to cover the end surfaces of the sealing layer 24, the diffusion layer 22, and the gas barrier member 20. However, At least covering the end face of the sealing layer 24 and covering the end face of the sealing layer 24 and the diffusion layer 22.

The end surface sealing member 64 may be formed in the form of the sealing laminate 10 or may be formed after the sealing laminate 10 is bonded to the organic electronic laminate 12.

6 (A), the end surface of the sealing layer 24 is covered with the sealing member 64, but the present invention is not limited thereto. The organic electronic device 70 , The end surface of the sealing layer 24 may be covered with the diffusion layer 74. [ 6 (B), the end surface of the diffusion layer 74 covering the end surface of the sealing layer 24 may be covered with the end surface sealing member 64.

That is, the sealing laminate 72 of the organic electronic device 70 shown in Fig. 6 (B) differs from the sealing laminate 72 of the sealing layer 24 in the sealing laminate 72 of the organic electronic device 70 in that the surface of the sealing layer 24 other than the surface on the side of the organic electronic laminate 12 And the end surface sealing member 64 covers the end surface of the diffusion layer 74. [

As described above, the end surface of the sealing layer 24 or the end surface of the diffusion layer 74 is covered with the end surface sealing member 64 to reduce the moisture penetrating the sealing layer 24, and the sealing layer 24 absorbs moisture, It is possible to make the organic electronic device more longevity.

In addition, by covering the end surface of the sealing layer 24 with the diffusion layer 74, it is possible to more appropriately diffuse the moisture intruding from the end face, to prevent the moisture from being absorbed by a part of the sealing layer 24, It is possible to more uniformly utilize the hygroscopicity of the water absorbent material 24. Therefore, it is possible to delay the arrival of moisture in the organic electronic element 32 and to stably protect the organic electronic element 32 for a long period of time, thereby making the organic electronic device more longevity.

1, in order to seal the organic electronic laminated body 12 using the gas barrier member 20 such as a glass plate, a metal plate, or a gas barrier film, the gas barrier member 20 (10) formed by laminating a sealing layer (24) as an adhesive layer on an organic electronic laminate (12) and forming the sealing laminate (10) on the organic electronic laminate (12) However, the present invention is not limited thereto, and the layers may be sequentially stacked.

That is, in the organic electronic device, after the sealing layer 24 having hygroscopic property is laminated on the element substrate 30 on which the organic electronic element 32 is formed, the diffusion layer 22 is laminated on the sealing layer 24, And an inorganic layer which is a barrier film covering these layers may be formed.

As described above, in the case of a structure in which a barrier film is directly formed, it is necessary to form a barrier film at a low temperature so as not to damage the organic electronic device. As a result, it is difficult to form a thick inorganic film, and defects are easily generated in the barrier film. When a defect occurs in the barrier film, only the sealing layer in the vicinity of the defect absorbs moisture and deactivates with time, so that the organic electronic device can not be sufficiently protected.

On the other hand, according to the structure of the present invention, even when the barrier film is directly formed, moisture penetrating from the defects of the barrier film is diffused by the diffusion layer 22 to effectively absorb the moisture of the entire sealing layer 24 can do. Therefore, the organic electronic device 32 can be stably protected for a long period of time, and the organic electronic device 50 can be lengthened.

The sealing laminate and the organic electronic device of the present invention have been described in detail above. However, the present invention is not limited to the above-described embodiments, and various modifications and changes may be made within the scope of the present invention Of course, of course.

Example

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.

[Example 1]

As Example 1, the organic electronic device 60 shown in Fig. 6 (A) was produced. Further, the organic electronic device 60 was made in the bottom emission type.

≪ Organic electronic laminate &

As the element substrate 30, a non-alkali glass substrate having a thickness of 500 mu m was used.

As shown in Fig. 7 (A), the element substrate 30, which is masked at both ends in a substantially C-shape and masked, is loaded in a general sputtering apparatus, and ITO (Indium Tin Oxide Oxidation Indium tin) was used as a target, and a transparent electrode 42 made of ITO thin film with a thickness of 0.2 m was formed by DC magnetron sputtering. The width of the transparent electrode 42 in the vertical direction in the region where the organic electroluminescent layer 40 is formed, that is, the width of the transparent electrode 42 indicated by h ₁ in the figure, is 23 mm.

Next, the following organic compounds were sequentially formed on the element substrate 30 on which the electrodes were formed by the vacuum evaporation method to form the organic electroluminescence layer 40. 7 (B), the edge portion was masked, and the organic electroluminescence layer 40 was formed to have a size of 30 mm × 30 mm in the approximate center of the element substrate 30.

First, HAT-CN was formed into a hole injection layer with a film thickness of 10 nm by a vacuum deposition apparatus. Next, a hole transport layer (? -NPD: Bis [N- (1-naphthyl) -N-phenyl] benzidine] was formed to a film thickness of 500 nm. A luminescent layer doped with 10% of Ir (ppy) 3 (Tris (2-phenylpyridinato) iridium) using CBP (4,4'-Bis (carbazol-9- yl) biphenyl) . Next, a layer of BAlq (Bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolate) -aluminium (III)) as a hole blocking layer was formed to a film thickness of 10 nm and Alq3 8-hydroxy-quinolinato) aluminum layer was formed to a thickness of 40 nm to form an organic electroluminescent layer 40.

The device substrate 30 on which these layers are formed is masked at both ends as shown in Fig. 7 (C), loaded into a vacuum evaporation apparatus, formed with a 0.5 nm-thick lithium fluoride layer by vacuum deposition, A reflection electrode 44 made of metal aluminum having a thickness of 200 nm was formed. The width h ₂ of the reflective electrode 44 in the left-right direction shown in Fig. 7 (C) was set to 23 mm.

That is, the size of the region of the organic electroluminescent layer 40 functioning as a light emitting layer, that is, the size of the organic electronic device 32, was set to 23 mm x 23 mm.

Next, a passivation film made of alumina was formed on the element substrate 30 on which the organic electronic element 32 was formed by reactive sputtering, and the organic electronic laminate 12 was produced.

The alumina film was formed by reactive sputtering using metal aluminum as a target and oxygen gas and argon gas as process gases. The thickness of the alumina film was set to 100 nm.

<Sealing laminate>

(Gas barrier film)

As the gas barrier film 20a, a film laminated with the gas barrier support 26, the organic layer 27, and the inorganic layer 28 as shown in Fig. 3 was used. The size of the gas barrier film 20a was 40 x 40 mm. That is, FIG. 7 (D), since the laminated body seal, the distance to the end of the organic electronic device _{(32) (t 1, t} 2) as shown in, has to 8.5mm.

The gas barrier film 20a was produced as follows.

As the gas barrier support 26, a 100 μm thick PET film (Cosmo Shine A4100, manufactured by Toyo Boseki Co., Ltd.) was used.

Next, an organic layer 27 was formed on the support 26 for gas barrier. The organic layer 27 was coated with a material for the gas barrier support 26 by a coating method, dried, and irradiated with ultraviolet rays to carry out polymerization to form a film having a thickness of 2 탆.

The coating material for forming the organic layer 27 was prepared by mixing TMPTA (manufactured by Daicel-Cytec), photopolymerization initiator (Irg184, manufactured by Chiba Chemicals), and silane coupling agent (KBM5103 manufactured by Shinsei Silicone Co., Ltd.) Was added thereto. That is, the organic layer 27 is a layer formed by polymerizing TMPTA.

The addition amount of the photopolymerization initiator was 2% by mass with the exception of the organic solvent, and the addition amount of the silane coupling agent was 10% by mass excluding the organic solvent (that is, the organic compound in the solid content was 88% by mass). The solid content concentration of the paint obtained by diluting the components blended in these ratios with MEK was 15 mass%.

Next, an inorganic layer 28 having a thickness of 50 nm was formed on the organic layer 27 by plasma CVD.

Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ) and hydrogen gas (H ₂ ) were used as the raw material gas. The supply amount of the gas was 100 sccm for the silane gas, 200 sccm for the ammonia gas, 500 sccm for the nitrogen gas, and 500 sccm for the hydrogen gas. The forming pressure was set at 50 Pa. That is, the inorganic layer 28 is a silicon nitride film.

The plasma excitation power was set to 3000 W at a frequency of 13.56 MHz. The bias power was set to 500 W at a frequency of 400 kHz.

A water vapor permeability of the gas barrier film (20a) are ^{produced, 1 × 10 -5 [g /} (m 2 · day)] was.

(Diffusion layer)

A material was applied onto the inorganic layer 28 of the gas barrier film 20a by a coating method and dried and cured to form a diffusion layer 22 of 20 mu m in thickness made of triacetylcellulose (TAC).

The paint forming the diffusion layer 22 was prepared by adding triacetyl cellulose and ethyl acetate as a solvent.

In addition, the water vapor permeability (WVTR) of the diffusion layer 22 in the 60 ℃, 90% humidity, temperature, thickness of 100μm, was ^{700 [g / (m 2 ·} day)].

(Sealing layer)

Next, a material was coated on the diffusion layer 22 by a coating method, followed by drying and curing to form a sealing layer 24 having a thickness of 20 占 퐉 to prepare a sealing laminate 10. [

The coating material for forming the sealing layer 24 is a mixture of a modified epoxy resin (NXR5516, manufactured by Naga Seiyaku Kogyo K.K.) and MEK (methyl ethyl ketone), and a drying agent such as aluminum oxide 2-ethylhexanoate Ltd., A00) was added.

The proportion of the desiccant was 30% by mass, excluding the organic solvent. The viscosity of the paint obtained by diluting the components blended in these ratios with MEK was 10 mPa · s.

In addition, a die coater was used for application. And adjusted to have a thickness of 10 mu m after drying.

In addition, the water vapor permeability (WVTR) of the sealing layer 24 in the 60 ℃, 90% humidity, temperature, thickness of 100μm, was ^{16 [g / (m 2 ·} day)].

&Lt; Organic electronic device &

The resulting sealing laminate 10 was adhered to the organic electronic laminate 12.

After the adhesion, ultraviolet rays were irradiated to cure the sealing layer 24. The dose of ultraviolet rays was set at about 3000 mJ / cm ² .

Thereafter, the end face of the sealing laminate 10 was sealed with the end face sealing member 64.

The material of the side-surface sealing member 64 was modified with epoxy resin (NXR5516, Nagaseishan Kogyo Co., Ltd.), and then cured by ultraviolet irradiation. The dose of ultraviolet rays was set at about 3000 mJ / cm ² .

After irradiation with ultraviolet rays, a curing process was performed at 80 DEG C for one hour to produce an organic electronic device 60. [

[Example 2]

An organic electronic device 60 was fabricated in the same manner as in Example 1 except that the material of the diffusion layer 22 was changed to polydimethylsiloxane (PDMS).

As a coating material for the PDMS layer, 20% by mass of a polymerizable polydimethylsiloxane (UV9300, Momentive Performance Materials Japan Ltd.), 4-isopropyl-4'-methyldiphenyliodonium tetrakis Heptane solution containing 0.1% of bis (pentafluorophenyl) borate (I0591, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was prepared.

This coating material was applied to the surface of the gas barrier film 20a and subjected to drying / UV irradiation treatment to form the diffusion layer 22.

Water vapor permeability of the diffusion layer ^{22, 1000 [g / (m 2} · day)] was higher.

[Example 3]

An organic electronic device 60 was produced in the same manner as in Example 1 except that an OCA tape (thickness: 25 mm, manufactured by Sumitomo 3M Limited) was used as the diffusion layer 22.

Water vapor permeability of the diffusion layer 22, was ^{500 [g / (m 2 ·} day)].

[Example 4]

An organic electronic device 60 was produced in the same manner as in Example 1, except that the material of the sealing layer 24 was changed to an epoxy compound shown below.

(YL980 manufactured by Mitsubishi Kagaku Kabushiki Kaisha), a polymerization initiator (IRGACURE 250, manufactured by BASF), and aluminum oxide 2-ethylhexanoate (manufactured by Hope Seiyaku Kabushiki Kaisha, Ltd.) as a desiccant, Ltd., A00) was added to MEK to prepare.

The proportion of the drying agent and the polymerization initiator was 30% by mass and 5% by mass, respectively, except for the organic solvent.

The water vapor permeability of the sealing layer 24 was 60 g / (m ² · day).

[Example 5]

An organic electronic device 60 was fabricated in the same manner as in Example 4 except that the material of the diffusion layer 22 was changed to the same PDMS as that in Example 2. [

[Example 6]

An organic electronic device 60 was fabricated in the same manner as in Example 4 except that the same OCA tape as that used in Example 3 was used as the diffusion layer 22.

[Example 7]

An organic electronic device 60 was fabricated in the same manner as in Example 1, except that the material of the sealing layer 24 was changed to the acrylic compound shown below.

(Shin-Nakamura Kagaku Kogaku Co., Ltd. A-DPH), a polymerization initiator (IRGACURE 184, manufactured by BASF), and a drying agent such as aluminum oxide 2-ethylhexanoate (available from Hope Seiyaku Co., Ltd.) was added to MEK to prepare a solution.

The proportion of the drying agent and the polymerization initiator was 30% by mass and 5% by mass, respectively, except for the organic solvent.

The water vapor transmission rate of this sealing layer 24 was 40 [g / (m &lt; ² &gt; day)].

[Example 8]

An organic electronic device 60 was fabricated in the same manner as in Example 7 except that the material of the diffusion layer 22 was changed to the same PDMS as that in Example 2. [

[Example 9]

An organic electronic device 60 was produced in the same manner as in Example 7 except that the same OCA tape as that used in Example 3 was used as the diffusion layer 22.

[Comparative Example 1]

An organic electronic device was produced in the same manner as in Example 1 except that no diffusion layer was provided.

[Comparative Example 2]

An organic electronic device was produced in the same manner as in Example 4 except that no diffusion layer was provided.

[Comparative Example 3]

An organic electronic device was produced in the same manner as in Example 7 except that no diffusion layer was provided.

[Comparative Example 4]

An organic electronic device was fabricated in the same manner as in Example 1 except that the material of the diffusion layer was changed to a modified epoxy resin (NXR5516, manufactured by Naga Seiyaku Co., Ltd.).

The water vapor permeability of this diffusion layer was 16 g / (m ² · day).

[Comparative Example 5]

An organic electronic device was produced in the same manner as in Example 1 except that the material of the diffusion layer was changed to an epoxy compound shown below.

A bisphenol A type epoxy resin (YL980 manufactured by Mitsubishi Kagaku K.K.) and a polymerization initiator (IRGACURE 250 manufactured by BASF) were added to MEK as a coating material for an epoxy compound.

The proportion of the polymerization initiator was 5% by mass, excluding the organic solvent.

The water vapor permeability of this diffusion layer was 60 [g / (m ² · day)].

[Comparative Example 6]

An organic electronic device was produced in the same manner as in Example 1 except that the material of the diffusion layer was changed to the acrylic compound shown below.

Dipentaerythritol hexaacrylate (Shin-Nakamura Kagaku Kagaku K.K. A-DPH) and a polymerization initiator (IRGACURE 184, manufactured by BASF) were added to MEK as a coating material of the acrylic compound.

The proportion of the polymerization initiator was 5% by mass, excluding the organic solvent.

The water vapor transmission rate of this diffusion layer was 40 [g / (m ² · day)].

[Example 10]

An organic electronic device was produced in the same manner as in Example 1 except that the sealing member 64 was not provided.

[Example 11]

An organic electronic device was produced in the same manner as in Example 2 except that the end face sealing member 64 was not provided.

[Example 12]

An organic electronic device was produced in the same manner as in Example 3 except that the end face sealing member 64 was not provided.

[Comparative Example 7]

An organic electronic device was produced in the same manner as in Example 10 except that no diffusion layer was provided.

[Example 13]

Except that the size of the element substrate 30 was 25 mm × 25 mm and the size of the organic electronic device 32 was 2 mm × 2 mm and the size of the gas barrier film 20a was 6 × 6 mm, In the same manner, the organic electronic device 60 was produced. That is, the distance (t ₁ , t ₂ ) from the end surface of the sealing laminate to the end surface of the organic electronic device 32 was ₂ mm.

[Comparative Example 8]

An organic electronic device was produced in the same manner as in Example 13 except that no diffusion layer was provided.

[Example 14]

An organic electronic device 60 was fabricated in the same manner as in Example 3 except that the size of the gas barrier film 20a was 27 × 27 mm. That is, the distance (t ₁ , t ₂ ) from the end surface of the sealing laminate to the end surface of the organic electronic device 32 was ₂ mm.

[Comparative Example 9]

An organic electronic device was produced in the same manner as in Example 14 except that no diffusion layer was provided.

[Example 15]

An organic electronic device 60 was fabricated in the same manner as in Example 14 except that the same PDMS as that used in Example 2 was used as the material of the diffusion layer 22.

[Example 16]

An organic electronic device 60 was produced in the same manner as in Example 15 except that the sealing layer 24 was not provided with a drying agent.

[Example 17]

An organic electronic device 60 was fabricated in the same manner as in Example 16 except that the thickness of the sealing layer 24 was 10 mu m and the thickness of the diffusion layer 22 was 10 mu m.

[evaluation]

Durability tests were conducted on the produced organic electronic devices of Examples 1 to 17 and Comparative Examples 1 to 9. More specifically, the sample was allowed to stand under an environment at a temperature of 85 캜 and a humidity of 85%, and the time until the organic electronic device began to deteriorate was measured. The organic EL material was deteriorated by moisture at a predetermined time interval by applying a voltage of 7 V to the organic electronic device using an SMU2400 type source measuring unit manufactured by Keithley Inc. to observe the shape of the light emitting surface using a microscope , The deterioration of the organic electronic device, that is, the arrival of moisture in the organic electronic device, was judged by the presence or absence of light emission at the edge portion of the light emitting surface.

The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, the organic electronic device of the present invention has higher durability than the comparative example.

From the comparison of Examples 1 to 9 and Comparative Examples 4 to 6, it can be seen that Examples 1 to 9, in which the water vapor permeability of the diffusion layer is 5 times or more the water vapor permeability of the sealing layer, have high durability.

It can also be seen from the contrast between Example 13 and Example 14 that the main surface of the sealing layer exerts a higher effect in the large-sized embodiment. On the other hand, from the comparison of Comparative Example 8 and Comparative Example 9, it can be seen that there is no influence of the size of the main surface of the sealing layer when the diffusion layer is not provided. This is because even if a desiccant is contained, only a desiccant near the end face can be used.

From the contrast between Examples 1 to 3 and Examples 10 to 12, it can be seen that it is more preferable to have a one-sided sealing member.

From the comparison between Example 16 and Example 17, it is preferable that the total thickness of the sealing layer and the diffusion layer is smaller, more preferably 20 m or less.

From the above results, the effect of the present invention is clear.

10, 62, 72 sealing laminate
12 organic electronic laminate
20, 208 gas barrier member
22, 74 Diffusion layer
24, 206 sealing layer
30, 202 element substrate
32, 204 Organic electronic devices
40 organic electroluminescent layer
42 Transparent electrode
44 reflective electrode
50, 60, 70, 200 Organic electronic devices
64 side sealing member

Claims (14)

A gas barrier member having gas barrier properties,
A diffusion layer laminated on the gas barrier member,
And a sealing layer laminated on the diffusion layer,
Wherein the water vapor permeability of the diffusion layer is 5 times or more of the water vapor permeability of the sealing layer. The method according to claim 1,
Wherein the sealing layer has adhesiveness. The method according to claim 1 or 2,
And a cross-sectional sealing member covering at least an end face of the sealing layer. The method according to claim 1 or 2,
And the diffusion layer covers the end surface of the sealing layer. The method of claim 4,
And a cross-section sealing member covering at least an end face of the diffusion layer. The method according to any one of claims 1 to 5,
Wherein the sealing layer is made of a curable resin. The method according to any one of claims 1 to 6,
Wherein the sealing layer has hygroscopicity. The method according to any one of claims 1 to 7,
Wherein the diffusion layer comprises at least one selected from the group consisting of dimethyl siloxane, triacetyl cellulose and acrylic resin. The method according to any one of claims 1 to 8,
Wherein the gas barrier member is a gas barrier film having at least a gas barrier support made of a resin film and an inorganic layer, or glass. The method according to any one of claims 1 to 9,
Wherein the gas barrier member has a vapor transmissivity of 1 x 10 ^-4 [g / (m ² · day)] or less. The method according to any one of claims 1 to 10,
Wherein an area of the main surface of the sealing layer is 100 mm ² or more and a total thickness of the sealing layer and the diffusion layer is 50 탆 or less. A sealing laminate according to any one of claims 1 to 11,
An organic electronic element,
And an element substrate in this order. The method of claim 12,
Wherein the organic electronic device is an organic electroluminescent device having a reflective electrode, an organic electroluminescent layer, and a transparent electrode in this order. 14. The method of claim 13,
Wherein the reflective electrode is disposed on the element substrate side, and the transparent electrode is disposed on the sealing laminate.

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