JP6026331B2 - Organic EL laminate - Google Patents

Description

  The present invention relates to an organic EL laminate in which an organic EL device that protects a light emitting element with a passivation film is sealed with a sealing substrate.

  An organic EL device (OLED device) using an organic EL (Electro Luminescence) material is used for a display, a lighting device, or the like.

The organic EL material used for this organic EL device is very sensitive to moisture. For this reason, in the organic EL device, a space is formed by giving a concave shape to the sealing substrate, and a getter material is arranged in the space where the organic EL material is sealed to supplement intruding moisture. It has been broken.
In addition, as disclosed in Patent Document 1, moisture is prevented from entering by using a flexible metal film as a sealing substrate.
However, these methods can be used only in the bottom emission method in which the light extraction direction is on the element substrate side on which the organic EL material is formed, and in the top emission method in which the light extraction direction is on the sealing substrate side. I can't.

On the other hand, as shown in Patent Document 2 and Patent Document 3, a light-emitting element (organic EL element) using an organic EL material, and providing a gas barrier property thereto, prevents deterioration of the organic EL material due to moisture. A method has been developed.
Specifically, a light-emitting element having an organic EL material or an electrode is covered on an element substrate with a passivation film (protective film) having gas barrier properties, and a sealing substrate is formed on the passivation film using an adhesive. The organic EL element is prevented from being deteriorated by moisture by using a laminated structure (organic EL laminated body) formed by adhering to each other.

In such an organic EL laminated body, examples of the passivation film forming material include inorganic materials such as silicon nitride, silicon oxide, and silicon oxynitride that exhibit gas barrier properties.
Examples of the material for forming the sealing substrate include glass, plastic, quartz, resin, metal, and the like.

JP 2001-118674 A JP 2010-198926 A Japanese Patent No. 5036628

  However, according to the study of the present inventor, even when the light-emitting element is covered with a passivation film and glass having a high gas barrier capability is used as a sealing substrate, moisture from the end face of the enclosed adhesive It has been found that moisture penetrates the passivation film and deteriorates from the edge portion of the organic EL material due to the intrusion.

  In order to suppress the intrusion of moisture from the end face, it is conceivable to increase the distance from the end face of the adhesive to the organic EL material. However, an organic EL device used as a display, particularly a mobile organic EL device such as a mobile phone, has a need to reduce the edge and increase the ratio of the screen to the product size. Therefore, it is difficult to increase the distance from the end portion to the organic EL material.

  Alternatively, it may be possible to increase the thickness of the passivation film. However, forming a thick inorganic film under conditions where the passivation film is formed at a low temperature so as not to damage the organic EL material is very inefficient and leads to an increase in cost.

Further, there is a demand for lightening and thinning the organic EL device. However, if metal or glass is used as the sealing substrate, the organic EL device becomes heavy and thick. Therefore, in order to better reduce the weight and thickness of the apparatus, it is advantageous to use a plastic film rather than using glass or the like as the sealing substrate.
However, according to the inventor's study, when an organic EL device in which a light-emitting element is covered with a passivation film is sealed with a plastic film as a sealing substrate, although weight reduction and thinning can be achieved, Delamination between layers, deterioration of the light emitting element due to the plastic film, and the like occur.

  The object of the present invention is to solve such problems of the prior art, while reducing the weight and thickness, preventing moisture from entering from the end, and preventing delamination between layers. Another object of the present invention is to provide an organic EL laminate that can more suitably prevent deterioration of a light-emitting element due to moisture or the like.

  In order to solve this problem, the present invention is to bond a light emitting element using an organic EL material, an organic EL device having a passivation film covering the light emitting element, and a transparent sealing substrate with an adhesive. The organic EL laminate is a top emission type in which the organic EL device emits light toward the sealing substrate side, and the sealing substrate includes an inorganic film and a base of the inorganic film on the support. It is a gas barrier film that has one or more combinations with an organic film, the surface layer is an inorganic film, the passivation film and the inorganic film on the surface face each other, and the organic EL device and the gas barrier film are bonded by an adhesive The adhesive is filled in the entire area between the passivation film and the surface inorganic film, and the passivation film at the end of the organic EL device. The gap between the surface of the inorganic film is in the position of the light emitting element, to provide an organic EL laminate, characterized in that narrower than the gap between the passivation film and the surface of the inorganic film.

Here, the edge distance L, which is the distance from the end of the organic EL device to the light emitting element, is preferably 5 mm or less.
Further, the ratio between the edge distance L, which is the distance from the edge of the organic EL device to the light emitting element, and the opening height d, which is the gap between the passivation film and the inorganic film on the surface, is d / It is preferable that L ≦ 0.1.
Moreover, it is preferable that the passivation film and the inorganic film of at least the surface layer of the gas barrier film are formed of the same material.

Moreover, it is preferable that the thickness of the adhesive agent in the edge part of an organic EL device is 1 micrometer-100 micrometers.
Moreover, it is preferable that the thickness of the adhesive in the position of a light emitting element is 2 micrometers-200 micrometers.

Further, the adhesive has a silane coupling agent, the passivation film and the surface inorganic film are silicon compound films, and silicon having at least one of —O group and —OH group introduced on the surface thereof. It is preferred to have a compound.
The passivation film and the surface inorganic film are preferably silicon nitride films.
Further, the thickness of the passivation film is preferably 10 μm or less.

Moreover, it is preferable that the thickness of the organic film of a gas barrier film is 0.5 micrometer-5 micrometers.
The gas barrier film preferably has a plurality of inorganic films, and all the inorganic films are preferably formed of the same material.

  According to the present invention, it is possible to reduce the weight and thickness of the organic LE laminate, to prevent moisture from entering from the end portion, and to prevent delamination between layers. The deterioration of the light emitting element due to the above can be suitably prevented.

It is a figure which shows notionally an example of the organic electroluminescent laminated body of this invention. (A) And (B) is a figure which shows notionally another example of the gas barrier film used for the organic electroluminescent laminated body of this invention. It is the elements on larger scale which show conceptually the structure of the edge part of the organic electroluminescent laminated body shown in FIG. It is the elements on larger scale which show notionally the structure of the edge part of the other example of the organic electroluminescent laminated body of this invention.

  Hereinafter, the organic EL laminate of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

In FIG. 1, an example of the organic electroluminescent laminated body of this invention is shown notionally.
As shown in FIG. 1, the organic EL laminate 10 of the present invention is obtained by bonding an organic EL device 12 having a light emitting element 24 using an organic EL material and a gas barrier film 14 with an adhesive 16. It is. Moreover, the organic EL laminated body 10 of this invention has the shape where the gap | interval between the gas barrier film 14 and the organic EL device 12 was restrict | squeezed in the edge part.

In the organic EL laminate 10 of the present invention, the organic EL device 12 is the same as a known organic EL device in which a light emitting element 24 is formed on an element substrate 20 and the light emitting element 24 is covered with a passivation film 26. It has a configuration.
Therefore, in the present invention, the organic EL device 12 has a light-emitting element 24 using an organic EL material and a passivation film 26 that covers the light-emitting element 24 in order to protect it from moisture, oxygen gas, or the like. All known organic EL devices (OLED devices) used in organic EL devices such as various organic EL displays and organic EL lighting devices can be used.

In the organic EL laminate 10 of the present invention, as the element substrate 20, all element substrates used in various organic EL devices can be used. Specifically, an element substrate made of glass, plastic, metal, ceramic, or the like is exemplified.
Here, in the organic EL laminated body of the present invention, it is preferable that moisture or the like can be prevented from passing through the element substrate 20 and reaching the light emitting element 24 in order to prevent deterioration of the light emitting element due to moisture or the like. Therefore, the element substrate 20 is preferably a substrate made of a material having a low content of moisture or the like and a low transmittance of moisture or the like, such as glass or metal.

Here, the organic EL laminate 10 of the present invention has an organic / inorganic laminate structure in which an organic film 32 and an inorganic film 34 described later are laminated as a sealing substrate for sealing the organic EL device 12. A gas barrier film 14 is used. Therefore, the organic EL laminated body 10 of the present invention is used in a top emission type organic EL device that emits light from the side opposite to the element substrate 20 (gas barrier film 14 side).
When the organic EL device is a top emission type, the element substrate 20 does not need to have light transmittance. Therefore, when the organic EL laminate 10 of the present invention is used in a top emission type organic EL device, the element substrate 20 is an aluminum foil having an anodized film on the surface, or a laminate of aluminum foil and polyimide. For example, a flexible metal film (metal plate) having an insulating layer may be used. In the present invention, since the gas barrier film 14 is used as the sealing substrate, a flexible organic EL display, an organic EL lighting device, or the like can be suitably manufactured by using such a metal film as the element substrate 20.

  Alternatively, a light transmissive material such as glass may be used as the element substrate 20 so that light is emitted also to the element substrate 20 side, and light is emitted from both sides.

As described above, in the organic EL laminate 10 of the present invention, the organic EL device 12 is a known organic EL device.
Therefore, the light emitting element (organic EL element) 24 formed on the element substrate 20 includes a light emitting part (light emitting layer) made of an organic EL material, an electrode, a hole injection layer, a hole transport layer, an electron transport layer, an electron. This is a known light-emitting element using an organic EL material having an injection layer and the like.
The light emitting element 24 may be formed by a known method according to the use or size of the organic EL laminate 10.

In the organic EL device 12, a passivation film (protective film) 26 is formed so as to cover the light emitting element 24 (or further, the surface of the element substrate 20).
The passivation film 26 is for preventing moisture, oxygen, or the like from reaching the light emitting element 24 and degrading the light emitting element 24 (particularly, organic EL material).

As the passivation film 26, various films (layers) made of a material that exhibits gas barrier properties, which are used in known organic EL devices, 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 preferably exemplified. Among them, a film made of silicon nitride is preferably exemplified in terms of high gas barrier properties and optical characteristics when used in a top emission type.
The passivation film 26 may be formed by a known method corresponding to the film forming material.

  As will be described in detail later, in the present invention, the passivation film 26 is preferably formed of the same material as the inorganic film 34 on the surface layer of the gas barrier film 14 described later.

In addition, the passivation film 26 is made of a silicon compound, and it is preferable that an —O group and / or an —OH group, particularly an —OH group, be introduced on the surface (the surface on the gas barrier film side). In particular, it is preferable that the passivation film 26 is formed of silicon nitride, and —O groups and / or —OH groups, particularly —OH groups are introduced into the surface thereof.
A suitable organic EL device 12 (passivation film 26) and an adhesive are obtained by introducing —O groups or —OH groups on the surface of the passivation film 26, and the adhesive 16 described later contains a silane coupling agent. 16 can be obtained. This will be described in detail later.

The passivation film 26 made of a silicon compound is usually formed by a vapor deposition method (vapor deposition method) such as plasma CVD or sputtering while maintaining a temperature at which the light emitting element 24 is not damaged.
Here, in a film made of a silicon compound formed by a low-temperature vapor deposition method, not all silicon is a target compound such as silicon nitride, and silicon having an unbonded bond is also included. Exists. In particular, a large amount of silicon having unbonded bonds is present on the surface of the film. Therefore, after the passivation film 26 is formed, if the surface of the film is exposed to air (atmosphere), -O groups or -OH groups are bonded to the unbonded bonds, and the surface of the passivation film 26 is- O groups and —OH groups, in particular —OH groups, can be introduced.

In the organic EL laminated body 10 of the present invention, the thickness of the passivation film 26 may be appropriately set according to the use, size, etc. of the organic EL laminated body 10.
In general, the thicker the passivation film 26, the higher the protection performance of the light emitting element 24 by the passivation film 26 against moisture and the like.
However, in the organic EL device 12, the passivation film 26 cannot be formed at a high temperature in order to prevent the light emitting element 24 from being damaged. Therefore, it takes time and labor to form the thick passivation film 26, which increases the cost. In addition, since the passivation film 26 is a film made of an inorganic material, if the passivation film 26 is too thick, damage such as cracking occurs naturally due to its internal stress.

Here, in the organic EL laminate 10 of the present invention, a high-performance gas barrier film 14 having an organic / inorganic laminate structure described later is used as a sealing substrate with the inorganic film 34 facing the passivation film 26 side. Therefore, even if the passivation film 26 is thinned, the light emitting element 24 can be sufficiently prevented from being deteriorated by moisture or the like.
Considering the above points, in the organic EL laminated body 10 of the present invention, the thickness of the passivation film 26 is preferably 10 μm or less. In particular, it is preferably 5 μm or less, and more preferably 3 μm or less. Thereby, the organic EL laminated body 10 can be made thinner and thinner, and the cost can be reduced.

On the other hand, in the organic EL laminate 10, the gas barrier film 14 has an organic film 32 on the support 30, and an inorganic film 34 on the organic film 32.
The organic EL laminate 10 of the present invention is configured by the above-mentioned organic EL device 12 and the gas barrier film 14 being bonded to each other with an adhesive 16 so as to face the inorganic film 34 and the passivation film 26. The

In the organic EL laminate 10 of the present invention, the gas barrier film 14 has one or more combinations of the inorganic film 34 and the organic film 32 serving as the base of the inorganic film 34 on the support 30. In addition, the surface (the surface opposite to the support 30) is the inorganic film 34.
Therefore, in the organic EL laminated body 10 of the present invention, the gas barrier film 14 has two combinations of the inorganic film 34 and the underlying organic film 32 as in the gas barrier film 14a shown in FIG. It may be a thing, or may have three or more.

Moreover, although mentioned later, in the organic electroluminescent laminated body 10 of this invention, it is preferable to use the low retardation film whose retardation value is 300 nm or less as the support body 30 of the gas barrier film 14. FIG. The organic film 32 is usually formed by a so-called coating method.
Here, many low retardation films are easily dissolved by a solvent. Therefore, when a low retardation film is used as the support 30 and the organic film 32 is formed on the surface thereof by a coating method, the support 30 is dissolved by the organic solvent contained in the paint, and optical properties such as retardation fluctuations are obtained. Deterioration may occur.

As described above, when the support 30 may be dissolved during the formation of the organic film 32, the support is formed on the surface of the support 30 like the gas barrier film 14b shown in FIG. The protective inorganic film 34a for protecting 30 may be formed, and one or more combinations of the organic film 32 and the inorganic film 34 may be formed thereon. The protective inorganic film 34a may be the same as the inorganic film 34.
Furthermore, in the case where the protective inorganic film 34a is provided on the surface of the support 30 as described above, there is a mixed layer in which both components are mixed between the support 30 and the protective inorganic film 34a. May be. By having this mixed layer, damage to the gas barrier film 14b (particularly the inorganic film 34) due to changes in temperature and humidity can be suitably prevented. This mixed layer is formed by controlling etching of the support 30 by plasma and drawing of ions and the like by bias applied to the support 30 when the protective inorganic film 34a is formed by vapor deposition. it can.

In the organic EL laminate 10 of the present invention, as the support 30 of the gas barrier film 14, various types that are used as a support in a known gas barrier film can be used.
Among them, films made of various plastics (polymer materials / resin materials) are preferably used in that they are easy to make thinner and lighter and are suitable for making the organic EL laminate 10 flexible.
Specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, transparent polyimide, polyacrylate, polymethacrylate, cycloolefin polymer ( Suitable examples include plastic films made of cycloaliphatic polyolefins), cycloolefin copolymers, and triacetylcellulose.

Here, as described above, the organic EL laminate 10 of the present invention is used in a top emission type organic EL device. Therefore, considering the optical characteristics of the organic EL laminate 10, it is preferable to use a low retardation film with a retardation value (Reetardation) of less than 300 nm, particularly 200 nm or less, particularly 150 nm or less.
Further, in order to reduce the load on the passivation film 26 and the inorganic film 34 to be described later, and more preferably prevent deterioration of the light-emitting element 24 due to moisture or the like, the water permeability of the support 30 itself is low, and It is preferable that the amount of water is small. In particular, the water content of the support 30 is preferably 300 [g / m ² ] or less, and particularly preferably 200 [g / m ² ] or less.
Considering the above points, the support 30 is preferably exemplified by a plastic film made of polycarbonate, cycloolefin polymer, cycloolefin copolymer, triacetylcellulose, and transparent polyimide. In particular, a plastic film made of polycarbonate, a cycloolefin polymer, a cycloolefin copolymer, or the like is suitable. Among them, a plastic film made of a cycloolefin copolymer is preferably exemplified as the support 30.

What is necessary is just to set the thickness of the support body 30 suitably according to the use and magnitude | size of the organic electroluminescent laminated body 10. FIG. Here, according to the study of the present inventors, the thickness of the support 30 is preferably about 10 μm to 200 μm. By setting the thickness of the support 30 within this range, preferable results are obtained in terms of reducing the weight and thickness of the organic EL laminate 10.
The support 30 may be provided with functions such as antireflection, phase difference control, and light extraction efficiency improvement on the surface of such a plastic film.

An organic film 32 is formed on the support 30. The organic film 32 is a film made of an organic compound (a film (layer) containing an organic compound as a main component), and is basically obtained by crosslinking (polymerizing) monomers and / or oligomers.
The organic film 32 is a base layer of the inorganic film 34 that mainly exhibits gas barrier properties in the gas barrier film 14.

Since the gas barrier film 14 has the organic film 32 as the base, the organic film 32 also functions as a cushion for the inorganic film 34. Therefore, when the organic EL device 12 and the gas barrier film 14 are bonded to each other or when the organic EL device 12 receives an impact from the outside, the inorganic film 34 is damaged by the cushioning effect of the organic film 32. Can be prevented.
Thereby, in the organic electroluminescent laminated body 10, the gas barrier film 14 expresses gas barrier performance appropriately, and can prevent suitably the deterioration of the light emitting element 24 by a water | moisture content.

In addition, the gas barrier film 14 includes the organic film 32 that is the base of the inorganic film 34, thereby embedding irregularities on the surface of the support 30, foreign matters attached to the surface, and the like to form the inorganic film 34. Appropriate film surface. As a result, it is possible to form an appropriate inorganic film 34 with no gaps and without cracks or cracks on the entire film formation surface.
By having such an organic / inorganic laminated structure, the gas barrier film 14 obtains high gas barrier performance such that the water vapor transmission rate is less than 1 × 10 ⁻⁴ [g / (m ² · day)]. Can do. That is, the organic EL laminated body 10 of the present invention uses the gas barrier film 14 having an organic / inorganic laminated structure and high gas barrier performance as a sealing substrate, so that the passivation film 26 is as thin as 3 μm or less as described above. Even in this case, it is preferable to prevent the light emitting element 24 from being deteriorated due to moisture or the like.

In the gas barrier film 14, various organic compounds (resins / polymer compounds) can be used as a material for forming the organic film 32.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, thermoplastic resin, or polysiloxane, etc. An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.

Among them, the organic film 32 composed of a polymer of a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group is preferable from the viewpoint of excellent glass transition temperature and strength.
In particular, in addition to the above strength, the glass transition temperature is 120 ° C. mainly composed of acrylate and / or methacrylate monomers and oligomer polymers in terms of low refractive index, high transparency and excellent optical properties. The above acrylic resin and methacrylic resin are preferably exemplified as the organic film 32.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resin and methacrylic resin, which are mainly composed of acrylate and / or methacrylate monomers and oligomer polymers, are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.
By forming the organic film 32 with such an acrylic resin or methacrylic resin, the inorganic film 34 can be formed on the base having a solid skeleton, so that the inorganic film 34 having a denser and higher gas barrier property can be formed. .

The thickness of the organic film 32 is preferably 0.5 μm to 5 μm.
By setting the thickness of the organic film 32 to 0.5 μm or more, the effect as a cushion at the time of pressing at the time of bonding the organic EL device 12 and the gas barrier film 14 is sufficiently exhibited. Damage can be prevented more reliably. Further, by setting the thickness of the organic film 32 to 1 μm or more, the film formation surface of the inorganic film 34 is more appropriately made appropriate, and an appropriate inorganic film 34 free from cracks and cracks is formed on the entire film formation surface. A film can be formed across.
In addition, by setting the thickness of the organic film 32 to 5 μm or less, problems such as cracks in the organic film 32 and curling of the gas barrier film 14 due to the organic film 32 being too thick are preferably prevented. be able to.
Considering the above points, the thickness of the organic film 32 is more preferably 1 μm to 5 μm.

In addition, when it has the some organic film 32 like the gas barrier film shown to FIG. 2 (A), the thickness of the organic film 32 may be the same, or may mutually differ.
Moreover, when it has the some organic film 32, the formation material of each organic film 32 may be the same or different. However, from the viewpoint of productivity and the like, it is preferable to form all the organic films 32 with the same material.

The organic film 32 may be formed by a known method such as a coating method or flash vapor deposition.
Moreover, in order to improve adhesiveness with the inorganic film which becomes the lower layer of the organic film 32, the organic film 32 preferably contains a silane coupling agent.

An inorganic film 34 is formed on the organic film 32 with the organic film 32 as a base.
The inorganic film 34 is a film made of an inorganic compound (film (layer) containing an inorganic compound as a main component), and the gas barrier film 14 mainly exhibits gas barrier properties.
Moreover, in the organic EL laminated body 10 of this invention, the surface layer (film | membrane of the surface on the opposite side to the support body 30) of the gas barrier film 14 becomes the inorganic film | membrane 34. FIG.

As the inorganic film 34, various kinds of films 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 oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide and silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon nitride carbide; silicon carbides such as silicon carbide; hydrides thereof; mixtures of two or more of these; and Films made of inorganic compounds such as these hydrogen-containing materials are preferably exemplified.
In particular, a film made of a silicon compound is preferably exemplified in that it has high transparency and can exhibit excellent gas barrier properties. Among these, in particular, a film made of silicon nitride is preferable because it has high transparency in addition to more excellent gas barrier properties.

Here, in the organic EL laminated body 10 of this invention, it is preferable that the surface inorganic film 34 and the above-mentioned passivation film 26 are formed with the same material.
The surface inorganic film 34 and the passivation film 26 may be different. However, the inorganic film 34 and the passivation film 26 are bonded via the adhesive 16. Therefore, it is more strongly bonded by being formed of the same material. This will be described in detail later.

  In the case of having a plurality of inorganic films 34 (including the protective inorganic film 34a) as in the gas barrier films 14a and 14b shown in FIG. 2, only the surface inorganic film 34 is the same material as the passivation film 26. May be formed. That is, when a plurality of inorganic films 34 are provided, the materials for forming the inorganic films 34 may be different from each other. However, if productivity etc. are considered, it is preferable to form all the inorganic films | membranes 34 with the same material.

Further, when the inorganic film 34 is formed of a silicon compound, it is preferable that —O groups and / or —OH groups, particularly —OH groups, are introduced into the surface of the surface inorganic film 34. In particular, it is preferable that the surface inorganic film 34 is formed of silicon nitride, and —O groups and / or —OH groups, in particular —OH groups, are introduced on the surface thereof.
A gas barrier film 14 (inorganic film 34) and a suitable gas barrier film 14 are obtained by introducing —O groups or —OH groups on the surface of the surface inorganic film 34 and the adhesive 16 described later containing a silane coupling agent. Adhesion with the adhesive 16 can be ensured. This will be described in detail later.

What is necessary is just to determine the thickness of the inorganic film 34 suitably according to a forming material, the thickness which can express the target gas barrier property. According to the study of the present inventors, the thickness of the inorganic film 34 is preferably 10 to 200 nm.
By setting the thickness of the inorganic film 34 to 10 nm or more, the inorganic film 34 that stably expresses sufficient gas barrier performance can be formed. In addition, the inorganic film 34 is generally brittle, and if it is too thick, there is a possibility of causing cracks, cracks, peeling, etc. However, if the thickness of the inorganic film 34 is 200 nm or less, cracks will occur. Can be prevented.
In consideration of such points, the thickness of the inorganic film 34 is preferably 10 nm to 100 nm, and more preferably 15 nm to 75 nm.
In the case where the gas barrier film has a plurality of inorganic films 34 (including the protective inorganic film 34a) as in the example shown in FIG. 2, the thickness of each inorganic film 34 may be the same or different.

The inorganic film 34 is preferably film density of ^{2.1g / cm 3 ~2.7g / cm 3} . By setting the film density to 2.7 g / cm ³ or less, the flexibility of the inorganic film 34, that is, the gas barrier film 14 can be ensured. Therefore, as will be described later, the gas barrier film 14 can be easily bent so that the gap between the gas barrier film 14 and the organic EL device 12 is narrowed at the end. Further, by setting the film density to 2.1 g / cm ³ or more, high durability can be secured, and sufficient gas barrier properties can be secured over a long period of time.
Since the obtained the advantages more suitably, it is more preferable to be ^{2.3g / cm 3 ~2.6g / cm 3} .

The inorganic film 34 may be formed by a known method. Specifically, vapor phase deposition methods such as plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vacuum evaporation are preferably exemplified.
As with the previous passivation film 26, after the inorganic film 34 is formed by vapor deposition, the surface of the film is exposed to air, so that the surface of the inorganic film 34 has —O groups, —OH groups, in particular — OH groups can be introduced.

The adhesive 16 is for bonding the passivation film 26 and the inorganic film 34. The adhesive 16 is basically filled in the entire area between the organic EL device 12 and the gas barrier film 14. At this time, the adhesive 16 is filled so as to fill the irregularities on the surface of the passivation film 26.
In the organic EL laminate 10 of the present invention, the adhesive 16 may be appropriately selected according to the material for forming the passivation film 26 and the inorganic film 34 so that both can be bonded with sufficient adhesion. As an example, an epoxy adhesive and an acrylic adhesive 16 are exemplified.

  In addition, since the organic electroluminescent laminated body 10 of this invention is a top emission type, it is preferable to utilize the thing which has the high light transmittance for the adhesive agent 16. FIG. Further, it is preferable to use an adhesive 16 that does not emit outgas (or very little).

Here, in the organic EL laminated body 10 of this invention, it is preferable that the adhesive agent 16 contains a silane coupling agent.
In addition, as described above, it is preferable that the passivation film 26 and the inorganic film 34 that are not bonded by the adhesive 16 have -O groups and / or -OH groups introduced into the surface.
Thereby, the adhesiveness of the adhesive agent 16, and the passivation film 26 and the inorganic film 34 can be made higher.

As is well known, a silane coupling agent binds silicon to a hydrolyzable group such as an alkoxy group and an organic functional group that can be expected to react and interact with an organic substance such as an amino group. is there.
The silane coupling agent becomes -OH group by hydrolyzing the hydrolyzable group, and this -OH group and -OH group on the surface of the inorganic compound are dehydrated and condensed, so that it is strong between the surface of the inorganic compound. Causes a covalent bond. Further, the silane coupling agent is firmly bound to the organic compound by copolymerization of an organic functional group and the organic compound. Thereby, the silane coupling agent improves the adhesion between the organic substance and the inorganic substance.

Here, according to the study of the present inventor, when the passivation film 26 and the inorganic film 34 are silicon compounds, an —O group, preferably an —OH group, is introduced into the surface thereof, such as “SiOH”. By maintaining the state, hydrolysis reaction and dehydration condensation of the silane coupling agent contained in the adhesive 16 are preferably generated.
That is, by introducing —OH groups or the like on the surfaces of the passivation film 26 and the inorganic film 34, —OH groups or the like are released from the surfaces of the passivation film 26 and the inorganic film 34, thereby causing a hydrolysis reaction of the silane coupling agent. The silicon compound and the silane coupling agent are bonded by a covalent bond by dehydration condensation, and higher adhesion between the adhesive 16, the passivation film 26, and the inorganic film 34 is obtained.

In general, when a silane coupling agent is used, the pH is adjusted by adding a pH adjusting agent (adding acid or alkali). However, when a pH adjuster is added to an adhesive containing a silane coupling agent, the above-described hydrolysis proceeds due to atmospheric humidity or water supply from an organic solvent, resulting in problems such as an increase in viscosity of the adhesive. .
On the other hand, according to the study of the present inventor, the adhesive 16 contains a silane coupling agent and introduces —O groups or OH groups into the surfaces of the passivation film 26 and the inorganic film 34 made of a silicon compound. In this case, high adhesion can be obtained without adjusting the pH by adding a pH adjusting agent. That is, according to this configuration, it is possible to eliminate the pH adjuster from the adhesive 16 that may cause inconvenience.

  In addition, the thickness of the adhesive 16 (the thickness of the film made of the adhesive) is a thickness that can reliably bond the organic EL device 12 and the gas barrier film 14 according to the size and use of the organic EL laminate 10. May be set as appropriate. Specifically, the thickness of the adhesive 16 at the position where the light emitting element is formed is preferably 2 μm to 200 μm.

As described above, the surface of the passivation film 26 has irregularities corresponding to the light emitting element 24, and the inorganic film 34 made of silicon nitride or the like is hard and brittle. Therefore, in consideration of damage such as cracking of the inorganic film 34, it is disadvantageous to directly contact the inorganic film 34 with the adhesive 16 to bond the organic EL device 12 and the gas barrier film 14.
On the other hand, by setting the thickness of the adhesive 16 (thickness of the adhesive 16 at the element position) to 2 μm or more, when pressing the organic EL device 12 and the gas barrier film 14, or during the organic EL When the laminated body 10 receives an impact from the outside, the inorganic film 34 can be protected by effectively acting the adhesive 16 as a cushion for preventing the inorganic film 34 from being damaged. Further, the adhesive 16 can embed irregularities on the surface of the passivation film 26. Thereby, the damage of the inorganic film 34 can be more reliably prevented by a synergistic effect with the action of the organic film 32 as a cushion.

On the other hand, considering the release of outgas from the adhesive, loss of flexibility when cured, light loss, and the like, the thickness of the adhesive 16 is preferably 200 μm or less.
In addition, the thickness of the adhesive 16 is more preferably 10 μm to 100 μm in terms of preventing damage to the inorganic film 34 by a more preferable cushion effect and obtaining an effect of reducing outgas. More preferably, the thickness is 60 μm.

In the organic EL laminate 10 of the present invention, the adhesion between the organic EL device 12 and the gas barrier film 14 with the adhesive 16 may be basically performed in the same manner as the adhesion of the sealing substrate in the known organic EL laminate.
That is, the adhesive 16 is applied to the surface of the inorganic film 34 of the gas barrier film 14 and / or the surface of the passivation film 26 of the organic EL device 12. Thereafter, the inorganic film 34 and the passivation film 26 are faced to each other, the organic EL device 12 and the gas barrier film 14 are laminated, and if necessary, pressed, heated, irradiated with ultraviolet rays, etc., and the adhesive 16 is cured. Then, they are bonded together.

  Here, the adhesive 16 usually does not have a gas barrier property. Therefore, in the organic EL laminate 10, moisture or the like enters from the end face of the adhesive 16, and this may reach the light emitting element 24 and deteriorate the light emitting element. Therefore, the organic EL laminate 10 of the present invention has a shape in which the gap between the organic EL device 12 (passivation film 26) and the gas barrier film 14 (inorganic film 34) is narrowed at the end (peripheral part). . In the following description, unless otherwise specified, the inorganic film 34 is the surface inorganic film 34.

FIG. 3 is a partial enlarged view conceptually showing the structure of the end portion of the organic EL laminate 10.
As shown in FIG. 3, the gas barrier film 14 is bent in the direction approaching the organic EL device 12 side at the periphery of the organic EL laminate 10. Furthermore, the gas barrier film 14 is bent again so as to be substantially parallel to the organic EL device 12 on the end side of the bent position. That is, at the end, the gap between the organic EL device 12 and the gas barrier film 14 is narrowed. In other words, the distance (height) from the surface of the passivation film 26 of the organic EL device 12 at the end surface to the inorganic film 34 of the gas barrier film 14 is smaller than the distance in the central region (position of the light emitting element 24). Further, the gas barrier film 14 is bent and disposed.

  By adopting a shape that narrows the gap between the organic EL device 12 and the gas barrier film 14 at the end, the surface area of the end surface of the adhesive 16 is reduced, and moisture and the like enter from the end surface of the adhesive 16. And deterioration of the light emitting element 24 can be prevented.

Here, the edge distance that is the distance from the end of the organic EL laminate 10 to the end of the light emitting element 24 is L, and the inorganic film 34 of the gas barrier film 14 from the passivation film 26 of the organic EL device 12 at the end. The edge distance L is preferably 5 mm or less, and the ratio d / L between the edge distance L and the opening height d is 0.1 or less. Preferably there is.
As described above, particularly when used as a mobile display such as a mobile phone, it is necessary to reduce the edge, but even if the edge distance L is reduced to 5 mm or less, the opening height By making d smaller than the distance between the passivation film 26 and the inorganic film 34 at the position of the light emitting element 24, it is possible to suitably prevent moisture and the like from entering from the end face. At that time, by setting the ratio d / L ≦ 0.1, it is possible to more suitably prevent moisture and the like from entering from the end face.

  Furthermore, in the organic EL laminated body 10 corresponding to a display having a screen size of 5 inches or less, the ratio d / L is preferably 0.002 to 0.1. A display having a screen size of 5 inches or less is used for a mobile device such as a mobile phone. Therefore, it is preferable that the ratio d / L is set to 0.002 to 0.1 to increase the ratio of the screen to the size of the product and to prevent the entry of moisture and the like from the end face.

Further, the passivation film 26 of the organic EL device 12 in the position of the light emitting element 24, when the sealing height d ₀ of the distance to the inorganic film 34 of the gas barrier film 14, the sealing height d ₀ and the opening height d The ratio d / d ₀ is preferably 0.01 to 0.9.
By setting the ratio d / d ₀ to 0.9 or less, it is possible to more suitably prevent moisture and the like from entering from the end face even when the edge distance is 5 mm or less.
Moreover, by setting the ratio d / d ₀ to be 0.01 or more, it is possible to prevent the barrier film from cracking and maintain the shape in a manner to follow the flexibility.

Moreover, it is preferable that opening height d shall be 1 micrometer-100 micrometers. Adhesion can be ensured by setting the opening height to 1 μm or more. On the other hand, by setting the opening height d to 100 μm or less, it is possible to suitably prevent intrusion of moisture or the like from the end face of the adhesive 16. Furthermore, from the above viewpoint, the thickness is preferably 5 to 50 μm, and more preferably 10 to 30 μm.
Moreover, it is preferable to arrange | position the bending position of the gas barrier film 14 in the outer side (end part side) rather than the light emitting element 24 of the end part side.

As described above, the organic EL laminated body 10 of the present invention has the organic EL device 12 having the passivation film 26 that covers the light emitting element 24 (or the surface of the element substrate 20) and the organic / inorganic laminated structure. The gas barrier film 14 whose surface layer is the inorganic film 34 is configured such that the passivation film 26 and the inorganic film 34 face each other and are bonded with an adhesive 16.
In addition, the organic EL laminate 10 of the present invention has a shape in which the gap between the organic EL device 12 (passivation film 26) and the gas barrier film 14 (inorganic film 34) is narrowed at the end (periphery). Have.

As described above, as the organic EL device (particularly, a top emission type organic EL device) 12, the passivation film 26 is formed so as to cover the light emitting element 24 formed on the element substrate 20, and the passivation film 26 is formed on the passivation film 26. A structure formed by sealing with a sealing substrate using an adhesive is known.
As also shown in Patent Document 1 and Patent Document 2, in such an organic EL device 12, various kinds of materials such as a glass plate and a plastic film are exemplified as the sealing substrate. Is used.

However, even when glass having a high gas barrier capability is used as the sealing substrate, moisture penetrates through the passivation film due to the intrusion of moisture from the end face of the sealed adhesive and deteriorates from the end of the light emitting element. End up.
It is conceivable to suppress the intrusion of moisture from the end face by increasing the distance from the end face of the adhesive to the light emitting element. However, since the organic EL laminate is used as a display, it is required to reduce the edge and increase the screen ratio, and it is difficult to increase the distance from the end surface of the adhesive to the light emitting element.
It is also conceivable to protect the light emitting element by increasing the thickness of the passivation film. However, forming a thick passivation film without damaging the light emitting element is very poor in productivity and causes an increase in cost.

  In recent years, there has been a growing demand for thinner and lighter organic EL devices. In addition, depending on the application, the organic EL device is also required to be flexible enough to be bent.

On the other hand, the organic EL laminate 10 of the present invention has an organic / inorganic laminate structure having an inorganic film 34 and a base organic film 32 as a sealing substrate, and the inorganic film 34 is a surface layer. The gas barrier film 14 is used.
Further, the organic EL device 12 and the gas barrier film 14 are bonded by the adhesive 16 in a state where the passivation film 26 and the inorganic film 34 are faced to each other. At this time, as a preferred embodiment, the passivation film 26 and the inorganic film 34 are formed of the same material.

Therefore, according to the present invention, since the flexible gas barrier film 14 is used as the sealing substrate, the gap between the organic EL device 12 and the gas barrier film 14 is formed by bending the gas barrier film 14 at the end. It can be formed to be narrow. Therefore, the area of the end surface of the adhesive 16 can be reduced, and entry of moisture and the like from the end surface of the adhesive 16 can be prevented.
Moreover, compared with the conventional organic electroluminescent laminated body which uses the glass plate etc. as a sealing substrate, weight reduction and thickness reduction can be achieved.

Moreover, as a preferable aspect, since the passivation film 26 and the inorganic film 34 are formed with the same material, they can be adhered to the adhesive 16 with the same force. As a result, the adhesive force between the two films can be made uniform to eliminate the stress difference, and the adhesive with the high adhesive force can be used by using an optimum adhesive for both the films. Therefore, delamination between the passivation film 26 and the adhesive 16 and between the adhesive 16 and the inorganic film 34 can be suitably prevented.
Further, the inorganic film 34 that exhibits gas barrier properties is used as a surface layer, and the passivation film 26 and the inorganic film 34 are faced to perform bonding. Therefore, even if the outgas is released from the support 30, the outgas is shielded by the inorganic film 34 and can be prevented from reaching the adhesive 16 and the passivation film 26. Therefore, according to the present invention, deterioration and delamination of the light emitting element 24 due to outgas from the support 30 can be prevented.

  Here, simply by using a flexible plastic film, the gap between the organic EL device 12 and the plastic film is narrowed at the end portion, the area of the adhesive on the end surface is reduced, and the end surface It is conceivable to prevent intrusion of moisture and the like from the water.

However, according to the study of the present inventor, when a plastic film is used as the sealing substrate, both the passivation film 26 (particularly a passivation film formed of a silicon compound) and the sealing substrate are compatible and sufficient. It is difficult to obtain adhesion.
As a result, delamination occurs between the passivation film 26 and the adhesive and / or between the adhesive and the plastic film, and a gas such as moisture remains in the form of bubbles at the interface. Therefore, even if there is a passivation film, the moisture and the like reach the light emitting element 24 over a long period of time, and the light emitting element 24 deteriorates.

Furthermore, as a result of the study, the present inventor has found that a gas such as moisture released from the plastic film (so-called outgas) also becomes a serious problem.
The plastic film contains various gases such as moisture. These gases are released from the film over time and become so-called outgas. This outgas also reaches the light emitting element 24 with the passage of time for a long time, like the gas in the previous bubble, and degrades the light emitting element 24. In addition, since the outgas also becomes a bubble in the space existing at the interface between the layers described above, adhesion deterioration, that is, delamination increases.
That is, when outgas is generated from the plastic film as the sealing substrate, delamination between layers and deterioration of the light emitting element 24 due to moisture and the like are accelerated.

  On the other hand, in this invention, the gas barrier film 14 which surface layer consists of the inorganic film | membrane 34 is used as a sealing substrate.

Here, as shown in FIG. 1, the surface of the passivation film 26 has irregularities corresponding to the light emitting elements 24. Further, since the inorganic film 34 made of silicon nitride or the like is hard and brittle, when it is directly pressed against another member, it easily causes damage such as cracks and cracks.
If the inorganic film 34 is damaged, moisture and the like permeate from here, so that the performance of the gas barrier film 14 is deteriorated.
Therefore, in general, considering the damage of the inorganic film 34, the surface layer of the gas barrier film 14 is used as the inorganic film 34, and the inorganic film 34 is brought into direct contact with the adhesive 16, so that the organic EL device 12 and the gas barrier Adhering to the film 14 is disadvantageous.

On the other hand, in order to protect the uppermost inorganic film 34, a gas barrier film having a protective organic film on the surface layer is also known. However, when the organic EL device 12 and the gas barrier film are bonded to each other by using the gas barrier film so that the protective organic film faces the passivation film 26, the same problem as the above-described plastic film occurs.
Further, in an organic EL device using an organic EL laminate, various functional layers such as a polarizing plate and a 1 / λ plate are formed on the organic EL laminate. Considering that these functional layers act as a protective film for the inorganic film 34, when the organic EL device 12 and the gas barrier film 14 are bonded with the support 30 facing the passivation film 26, the above-described plastic film is also obtained. Cause similar problems.

On the other hand, in the organic EL laminate 10 of the present invention, the gas barrier film 14 has the organic film 32 as a base of the inorganic film 34. Therefore, when the organic EL device 12 and the gas barrier film 14 are bonded together, the organic film 32 functions as a cushion for the inorganic film 34, and the inorganic film 34 can be protected to prevent damage.
In addition, since the appropriate inorganic film 34 can be formed by having the underlying organic film 32, the gas barrier film 14 has a water vapor transmission rate of less than 1 × 10 ⁻⁴ [g / (m ² · day)]. And high gas barrier performance. As a result, as described above, the cost can be reduced by reducing the thickness of the passivation film 26.

  Further, as described above, the layer of the adhesive 16 also functions as a cushion for the inorganic film 34. Considering the function as a cushion, the layer of the adhesive 16 is preferably thick. If the thickness of the adhesive 16 is increased, there is a risk that the intrusion of moisture from the end face may increase. However, in the present invention, the area of the end face of the adhesive 16 can be reduced as the end portion is narrowed. Accordingly, it is possible to prevent moisture from entering from the end face while thickening the adhesive 16 and suitably protecting the inorganic film 34.

  As described above, according to the organic EL laminate 10 of the present invention, in addition to lightening and thinning by using the gas barrier film 14 as a sealing substrate, delamination inside the organic EL laminate 10 is prevented, and In addition, the effect of using the gas barrier film 14 as a sealing substrate is sufficiently expressed, and further, the intrusion of moisture from the end of the adhesive 16 is prevented, and the cost is reduced by reducing the thickness of the passivation film 26. It is possible to more suitably prevent the light emitting element 24 from being deteriorated by moisture or the like, and as a result, it is possible to obtain the organic EL laminate 10 that exhibits the target performance for a long time.

Here, in the organic EL laminate 10 shown in FIG. 1, the end portion of the gas barrier film 14 is bent twice to narrow the gap between the organic EL device 12 and the gas barrier film 14. this is not the sole, squeezing the gap between the organic EL device 12 and the gas barrier film 14, the opening height d only has to be smaller than the sealing distance d _0.
For example, as shown in FIG. 4, the peripheral portion of the gas barrier film 14 is curved in the direction of the organic EL device 12 to narrow the gap between the organic EL device 12 and the gas barrier film 14 and reduce the opening height d. It is good also as a structure.
Note that the gap between the organic EL device 12 and the gas barrier film 14 between the organic EL device 12 and the gas barrier film 14 at the position of the light emitting element is outside the position of the light emitting element. It is preferable to make it smaller than the gap between.

  As mentioned above, although the organic EL laminated body of this invention was demonstrated in detail, this invention is not limited to the said Example, You may perform various improvement and a change in the range which does not deviate from the summary of this invention. Of course.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

[Example 1]
As Example 1, the organic EL laminated body 10 shown in FIG.

(Organic EL device)
As the element substrate 20, a glass substrate having a thickness of 500 μm was used.
The periphery of this element substrate 20 was masked with ceramics. Furthermore, the element substrate 20 subjected to masking is loaded into a general vacuum deposition apparatus, an electrode made of metal aluminum having a thickness of 100 nm is formed by vacuum deposition, and a lithium fluoride layer having a thickness of 1 nm is further formed. did.

Next, the following organic compounds were sequentially formed on the element substrate 20 on which the electrode and the lithium fluoride layer were formed by vacuum deposition.
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm

  Further, the element substrate 20 on which these layers are formed is loaded into a general sputtering apparatus, and an ITO thin film having a thickness of 0.2 μm is formed by DC magnetron sputtering using ITO (Indium Tin Oxide indium tin oxide) as a target. The transparent electrode which consists of was formed, and the light emitting element 24 using an organic EL material was formed.

The light-emitting element 24 has a size of 2000 μm × 2000 μm.
The edge distance L from the end of the element substrate 20 to the light emitting element 24 was 2.5 mm.

(Passivation film)
Next, the masking was removed, and a passivation film 26 made of silicon nitride was formed by a plasma CVD method on the glass substrate on which the organic EL element was formed.
Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as source gases. The supply amount of the source gas was 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The forming pressure was 50 Pa.
The plasma excitation power was 3000 W at a frequency of 13.56 MHz.
The passivation film 26 has a thickness of 3 μm on the light emitting element 24. In addition, after the passivation film 26 was formed, the surface of the film was exposed to the atmosphere, and —O groups and —OH groups were introduced to produce the organic EL device 12.

(Gas barrier film)
As the gas barrier film 14, a film in which a support 30, an inorganic film 34a, an organic film 32, and an inorganic film 34 are laminated as shown in FIG.
As the support 30, a cycloolefin copolymer (COC) film (F1 film, manufactured by Gunze Co., Ltd.) having a thickness of 100 μm was used. The water vapor transmission rate (WVTR) of this COC film was 2 [g / m ² · day].

Next, an inorganic film 34a having a thickness of 50 nm was formed on the support 30 by plasma CVD.
Silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ), and hydrogen gas (H ₂ ) were used as source gases. The gas supply amounts were 100 sccm for silane gas, 200 sccm for ammonia gas, 500 sccm for nitrogen gas, and 500 sccm for hydrogen gas. The forming pressure was 50 Pa. That is, the inorganic film 34a is a silicon nitride film.
The plasma excitation power was 3000 W at a frequency of 13.56 MHz. The bias power was 500 W at a frequency of 400 kHz.

Next, the organic film 32 was formed on the inorganic film 34a. The organic film 32 was formed by applying a material to the support 30 by a coating method, drying, and polymerizing by irradiation with ultraviolet rays to form a film having a thickness of 2 μm.
The coating material for forming the organic film 32 is MEK (methyl ethyl ketone), TMPTA (manufactured by Daicel-Cytec), photopolymerization initiator (Irg184, manufactured by Ciba Chemicals), and silane coupling agent (KBM5103, manufactured by Shin-Etsu Silicone). Added and prepared. That is, the organic film 32 is a layer formed by polymerizing TMPTA.
The addition amount of the photopolymerization initiator was 2% by mass in the concentration excluding the organic solvent, and the addition amount of the silane coupling agent was 10% by mass in the concentration excluding the organic solvent (that is, the organic compound in the solid content was 88% by mass). mass%). Moreover, the solid content concentration of the paint obtained by diluting the components blended in these ratios with MEK was 15% by mass.

Next, an inorganic film 34 having a thickness of 50 nm was formed on the organic film 32 by plasma CVD.
The inorganic film 34 was formed in the same manner as the inorganic film 34a described above except that the bias power was set to 300W. That is, the inorganic film 34 is a silicon nitride film. Further, after the inorganic film 34 was formed, the surface of the film was exposed to the atmosphere to introduce —O groups or —OH groups.

(adhesive)
Adhesive 16 is obtained by dissolving 48% of epoxy resin (JER1001), 48% of epoxy resin (JER152) and 4% of silane coupling agent (KBM502) in MEK to make a 50% weight solution. It was.
The adhesive 16 is applied to the gas barrier film 14 so as to have a predetermined thickness, and the solvent is sufficiently volatilized. Then, the adhesive 16 is bonded to the organic EL device 12 under an inert gas and left in an environment of 100 ° C. for 100 hours. And cured to produce an organic EL laminate 10.
At this time, pressing is performed such that the thickness of the adhesive 16 at the position of the light emitting element 24 (sealing height d ₀ ) is 50 μm, and the thickness of the adhesive on the end surface (opening height d) is 25 μm. The gas barrier film 14 and the organic EL device 12 were bonded. That is, d / L was set to 0.01.

(Evaluation)
Next, after measuring the overall luminance immediately after the production of the produced organic EL laminate 10, it was left for 200 hours in an environment of a temperature of 60 ° C. and a humidity of 90%, and then the light emitting element 24 was turned on, The luminance was measured again to determine the rate of luminance reduction. Also, the presence or absence of blackening (so-called dark spots) was confirmed with a microscope. Evaluation was performed according to the following criteria. As a result of the evaluation, no blackening or luminance reduction was observed (Evaluation AAA).
AAA: The luminance decrease was 1% or less, and no blackening was observed.
AA: The decrease in luminance was 1% or more and less than 3%.
A: The decrease in luminance was 3% or more and less than 5%.
B: The luminance decrease was 5% or more and less than 8%.
C: The brightness reduction was 8% or more and less than 10%.
D: The luminance reduction was 10% or more and less than 30%.
E: The decrease in luminance is 30% or more, and it can be easily visually confirmed that the emission is low visually.
Evaluation is acceptable up to C, and NG is below D.

[Example 2]
As Example 2, an organic EL laminate was manufactured in the same manner as Example 1 except that the opening height d was 1 μm and d / L was 0.0004.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was A. Since some dark spots were observed around the edge, the adhesive layer at the edge was thin, and it is considered that moisture entered slightly from a minute adhesion failure portion.

[Example 3]
As Example 3, an organic EL laminate was prepared in the same manner as Example 1 except that the opening height d was 50 μm, the sealing height d ₀ was 100 μm, and d / L was 0.02.
When this organic EL laminate was evaluated in the same manner as in Example 1, the evaluation was AA.

[Example 4]
As Example 4, an organic EL laminate was produced in the same manner as in Example 1 except that the opening height d was 100 μm, the sealing height d ₀ was 200 μm, and d / L was 0.04.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was B. Dark spots were seen at the edges and the entire surface. This is considered to be the influence of outgas due to the thick adhesive layer and the influence of penetration from the end due to the large opening height.

[Example 5]
As Example 5, an organic EL laminate was manufactured in the same manner as Example 1 except that the opening height d was 110 μm, the sealing height was d ₀ was 250 μm, and d / L was 0.044. .
When this organic EL laminate was evaluated in the same manner as in Example 1, the evaluation was C. Dark spots were seen at the edges and the entire surface. This is considered that the influence of outgas due to the thick adhesive layer and the influence of intrusion from the end due to the large opening height were considered.

[Example 6]
As Example 6, an organic EL laminate was produced in the same manner as in Example 1 except that the adhesive thickness at the position of the light emitting element was 250 μm.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was A. Some dark spots were seen on the entire surface, which is considered to be the effect of outgassing due to the thick adhesive layer.

[Example 7]
As Example 7, except that the sealing height d ₀ and 1.5μm was produced an organic EL laminate in the same manner as in Example 2.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was B. Since dark spots were observed on the entire surface, the thickness of the adhesive was thin, which is considered to be the effect of the surface inorganic film being destroyed by pressing.

[Example 8]
As Example 8, an organic EL laminate was produced in the same manner as in Example 1 except that the edge distance L was 1 mm and d / L was 0.05.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was A. A slight dark spot was observed at the edge, which is considered to be the effect of faster moisture arrival due to the shorter edge distance.

[Example 9]
As Example 9, an organic EL laminate was produced in the same manner as in Example 3 except that the edge distance L was 1 mm and d / L was 0.05.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was B. Dark spots were seen at the edges. It is considered that the effect of the fact that the amount of moisture intrusion is increased and the edge distance is short is remarkable due to the wide opening compared to Example 8.

[Example 10]
Example 10 is the same as Example 1 except that the opening height d is 85 μm, the sealing height d ₀ is 100 μm, the edge distance L is 0.8 mm, and d / L is 1.06. Thus, an organic EL laminate was produced.
When this organic EL laminate was evaluated in the same manner as in Example 1, the evaluation was C. This is probably because the opening height d was larger than the edge distance L, so that the moisture arrival was faster than in Examples 8 and 9.

[Example 11]
As Example 11, an organic EL laminate was produced in the same manner as in Example 1 except that an aluminum oxide film was formed as an inorganic film on the surface of the gas barrier film.
The aluminum oxide film was formed by reactive sputtering using metallic aluminum as a target and oxygen gas and argon gas as process gases. The thickness of the aluminum oxide film was 50 nm.
When this organic EL laminate was evaluated in the same manner as in Example 1, the evaluation was C. This is presumably because the difference in stress between the adhesive produced by the difference in the material between the inorganic film of the gas barrier film and the passivation film became significant and delamination occurred.

[Example 12]
As Example 12, an organic EL laminate was produced in the same manner as in Example 1 except that the adhesive did not contain a silane coupling agent.
When this organic EL laminate was evaluated in the same manner as in Example 1, the evaluation was C. This is presumably because the adhesion between the adhesive layer, the organic EL device and the gas barrier film was low and delamination occurred.

[Comparative Example 1]
As Comparative Example 1, an organic EL laminate was produced in the same manner as in Example 1 except that the surface inorganic film 34 of the gas barrier film was not formed. That is, a gas barrier film in which an inorganic film and an organic film were formed and the organic film was formed on the surface layer was used as a sealing substrate.
When the same evaluation as in Example 1 was performed on this organic EL laminate, the evaluation was D. This is considered to be an influence of outgas from the organic film of the gas barrier film.

[Comparative Example 2]
As Comparative Example 2, the thickness d ₀ of the adhesive at the position of the light emitting element and 200 [mu] m, except that the thickness d of the adhesive at the end face was 200 [mu] m was produced in the same manner as the organic EL laminate as Comparative Example 2 .
When this organic EL laminated body was evaluated in the same manner as in Example 1, dark spots were observed in the peripheral portion and the entire surface portion, the peripheral portion was completely blackened with a width of 1 mm, and light emission disappeared. Evaluation was E. This is thought to suggest that both outgas and end entry moisture are very high.

[Comparative Example 3]
As Comparative Example 3, a glass substrate having a thickness of 300 μm was used as the sealing substrate, the thickness d ₀ of the adhesive at the position of the light emitting element was set to 200 μm, the thickness d of the adhesive at the end surface was set to 200 μm, and d / An organic EL laminate similar to that of Example 1 was prepared except that L was 0.08.
When this organic EL laminate was evaluated in the same manner as in Example 1, the peripheral portion was completely blackened with a width of several hundreds of μm. Evaluation was E.
Further, when a glass substrate is used as the sealing substrate, there arises a problem that the whole becomes heavy and thick.
The results are shown in Table 1.

As described above, Examples 1 to 12, which are examples of the present invention, have no decrease in luminance or dark spots even after being allowed to stand for 200 hours, or are slight, preventing moisture from entering, It can be seen that deterioration is prevented.
On the other hand, in Comparative Examples 1 to 3, after 200 hours of standing, the luminance decreased near the end, and it was found that moisture could not be prevented from entering from the end face of the adhesive. Further, in Comparative Examples 1 and 2, a light emission failure occurs in the entire region, and it is understood that the deterioration of the light emitting element cannot be prevented by the outgas from the organic film.

Moreover, since the penetration | invasion of the water | moisture content from the end surface of an adhesive increases when the opening height d is large from the comparison of Examples 1-5, the comparison of Examples 8 and 9, etc., the opening height d is 1 μm to 100 μm is preferable, 5 μm to 50 is more preferable, and 10 μm to 30 μm is further preferable.
Further, from the comparison of Examples 1 to 7, when the sealing height d ₀ is large, there is an influence of outgas from the adhesive, and when the sealing height d ₀ is small, the surface layer is inorganic due to the unevenness of the light emitting element. Since the film is partially broken, it can be seen that the sealing height d ₀ is preferably 2 μm to 200 μm, more preferably 10 μm to 100 μm, and even more preferably 20 μm to 60 μm.
In addition, from the comparison with Examples 1 and 8, the comparison with Examples 3 and 9, etc., the shorter the edge distance L, the greater the influence of moisture intrusion from the end face of the adhesive, and thus the present invention is effective. I understand.
Further, from the comparison of Examples 1, 3, 8, 9, and 10, it can be seen that d / L is preferably 0.1 or less.
Further, it is understood from the comparison between Examples 1 and 11 that the inorganic film of the gas barrier film is preferably a silicon nitride film, and that the inorganic film and the passivation film of the gas barrier film are preferably made of the same material.
Further, it is understood from the comparison between Examples 1 and 12 that the adhesive preferably contains a silane coupling agent.
From the above results, the effect of the present invention is clear.

  It can be suitably used for an organic EL display, an organic EL lighting device, and the like.

DESCRIPTION OF SYMBOLS 10,100 Organic EL laminated body 12 Organic EL device 14 Gas barrier film 16 Adhesive 20 Element substrate 24 Light emitting element 26 Passivation film 30 Support body 32 Organic film 34 Inorganic film

Claims (11)

Organic EL formed by adhering a light- emitting element using an organic EL material, an element substrate supporting the light- emitting element, an organic EL device having a passivation film covering the light-emitting element, and a transparent sealing substrate. A laminate,
The organic EL device is a top emission type that emits light toward the sealing substrate side,
The sealing substrate is a gas barrier film having one or more combinations of an inorganic film and an organic film serving as a base of the inorganic film on a support made of a resin material , the surface layer being an inorganic film,
The passivation film and the inorganic film of the surface layer face each other, and the organic EL device and the gas barrier film are bonded by the adhesive,
The adhesive is filled in the entire area between the organic EL device and the gas barrier film ,
Furthermore, the gap between the passivation film and the inorganic film on the surface layer at the edge of the organic EL device is larger than the gap between the passivation film and the inorganic film on the surface layer at the position of the light emitting element. An organic EL laminate characterized by being narrow.   The organic EL laminate according to claim 1, wherein an edge distance L, which is a distance from an end of the organic EL device to the light emitting element, is 5 mm or less.   The ratio of the edge distance L, which is the distance from the edge of the organic EL device to the light emitting element, and the opening height d, which is the gap between the passivation film and the inorganic film of the surface layer at the edge, It is d / L <= 0.1, The organic electroluminescent laminated body of Claim 1 or 2.   The organic EL laminate according to any one of claims 1 to 3, wherein the passivation film and at least the surface inorganic film of the gas barrier film are formed of the same material.   The organic EL laminate according to any one of claims 1 to 4, wherein a thickness of the adhesive at an end portion of the organic EL device is 1 µm to 100 µm.   The organic EL laminate according to claim 1, wherein a thickness of the adhesive at a position of the light emitting element is 2 μm to 200 μm. The adhesive has a silane coupling agent;
The said passivation film and the inorganic film of the said surface layer are films | membranes of a silicon compound, and have a silicon compound by which at least one of -O group and -OH group was introduce | transduced on the surface. The organic electroluminescent laminated body as described in any one of.   The organic EL laminate according to any one of claims 1 to 7, wherein the passivation film and the inorganic film on the surface layer are silicon nitride films.   The thickness of the said passivation film is 10 micrometers or less, The organic electroluminescent laminated body of any one of Claims 1-8.   The organic EL laminate according to any one of claims 1 to 9, wherein a thickness of the organic film of the gas barrier film is 0.5 µm to 5 µm.   The organic EL laminate according to claim 1, wherein the gas barrier film has a plurality of the inorganic films, and all the inorganic films are formed of the same material.

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