JP2014143142A - Organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronic device in which an organic electronic element on a glass substrate is sealed.SOLUTION: The organic electronic device includes the glass substrate, the organic electronic element formed on a front surface of the glass substrate, and a barrier film bonded to the glass substrate. The barrier film is bonded to the glass substrate so as to seal the organic electronic element together with the glass substrate. The barrier film includes a base material, at least one organic layer, and at least one inorganic layer. At least part of an end of the barrier film is bonded to a rear surface of the glass substrate.

Description

  The present invention relates to organic electronic devices. The present invention particularly relates to an organic electronic device having a structure in which an organic electronic element on a glass substrate is sealed with a barrier film.

  Many organic electronic devices have been proposed in which organic electronic elements that are weak against water and oxygen are sealed with a barrier film. Sealing of an organic electronic element formed on a glass substrate is usually performed by bonding a barrier film with an adhesive, but the influence of moisture intrusion passing through the adhesive from the end is also great. Therefore, it is necessary to ensure the durability by sufficiently securing the distance between the organic electronic element and the edge of the barrier film to increase the moisture diffusion distance. On the other hand, the outer part of the organic electronic element on the substrate of the organic electronic device is a dead space and is preferably small.

  In relation to the above, Patent Document 1 discloses a technique for reducing the influence of moisture intrusion from the end by configuring the end of the barrier film provided on the organic electronic element so as to cover the end of the substrate. Is disclosed. Patent Document 2 describes a method for manufacturing a light-emitting device in which a light-emitting element is sealed with a bag-like film that includes an organic layer and an inorganic layer. Patent Document 3 describes a gas barrier excellent in flexibility.

Special table 2007-531238 gazette JP 2003-109756 A JP 2011-63851 A

  An object of the present invention is to provide an organic electronic device having a structure in which an organic electronic element on a glass substrate is sealed.

In the technique described in Patent Document 1, since the end portion of the barrier film is bonded from the front surface to the back surface of the substrate, the adhesive is maintained while keeping the distance between the organic electronic element and the edge of the barrier film short. It is possible to increase the diffusion distance of moisture that has entered from the end. In Patent Document 1, a metal foil is specifically described as a barrier film, and an end portion of the metal foil is curved to take the above structure.
The present inventors have attempted to provide an organic electronic device having a structure that can similarly seal an organic electronic element on a glass substrate and can efficiently perform light emission from the organic electronic element and light reception to the organic electronic element. The present invention has been completed.

That is, the present invention provides the following (1) to (17).
(1) A glass substrate, an organic electronic device formed on the surface of the glass substrate, and a barrier film adhered to the glass substrate, wherein the barrier film seals the organic electronic device together with the glass substrate. An organic electronic device bonded to the glass substrate,
The barrier film includes a substrate, at least one organic layer, at least one inorganic layer,
An organic electronic device in which at least a part of an end of the barrier film is bonded to the glass substrate on the back surface of the glass substrate.
(2) The organic electronic device according to (1), wherein at least a part of the end portion of the barrier film is bonded to the glass substrate on a back surface and a front surface of the glass substrate.

(3) The organic electronic device according to (1) or (2), wherein the thickness of the substrate is 50 μm or less.
(4) The organic electronic device according to (1) or (2), wherein the thickness of the base material is 25 μm or less.
(5) The organic electronic device according to any one of (1) to (4), wherein the inorganic layer is made of a silicon compound or an aluminum compound.
(6) The organic electronic device according to (5), wherein the inorganic layer includes one or more selected from the group consisting of silicon nitride, hydrogenated silicon nitride, and hydrogenated silicon oxynitride.
(7) The organic electronic device according to any one of (1) to (6), wherein the inorganic layer contains hydrogen of 25% atom or more and 30% atom or less.

(8) The organic electronic device according to any one of (1) to (7), wherein an outermost surface layer on the glass substrate side of the barrier film is an inorganic layer.
(9) The organic electronic device according to any one of (1) to (8), wherein an end portion of the glass substrate bonded to the barrier film on the back surface is chamfered.
(10) The organic electronic device according to (9), wherein an end portion of the glass substrate bonded to the barrier film on the back surface has an arc shape.
(11) The organic electronic device according to (10), wherein a radius of curvature of the arc is 0.2 mm or less.
(12) The organic electronic device according to (9), wherein an end portion of the glass substrate bonded to the barrier film on the back surface has a polygonal shape.
(13) The organic electronic device according to (12), wherein a minimum angle of the polygon is 135 degrees or more.

(14) The organic electronic device according to any one of (1) to (13), wherein the organic electronic element is an organic EL element.
(15) The barrier film has a shape of a rectangle 1;
The ends of the barrier film on two sides parallel to the Y direction of the rectangle 1 are bonded to the glass substrate on the back surface, and the glass substrate has a shape of the rectangle 2, and the barrier film is bonded. The organic electronic device as described in any one of (1)-(14) which exists in the edge part of 2 sides of the back surface which is parallel to the Y direction of the rectangle 2.
(16) The organic electronic device according to (15), wherein the edge of the barrier film is not bonded to the glass substrate on the back surface at two sides parallel to the X direction of the rectangle 1.
(17) The distance from the edge of the glass substrate on the two sides parallel to the Y direction of the rectangle 2 to the organic electronic element is from the edge of the glass substrate on the two sides of the rectangle 2 parallel to the X direction. The organic electronic device according to (15) or (16), which is shorter than the distance to the organic electronic element.

  According to the present invention, there is provided an organic electronic device having a structure in which an organic electronic element on a glass substrate is sealed with a film, and in particular, the influence of moisture intrusion from an end portion is reduced. In one embodiment of the present invention, it is possible to provide an organic electronic device in which an organic electronic element is sealed with a transparent and electrically insulating film.

It is a figure which shows an example of arrangement | positioning of the glass substrate and barrier film in the manufacturing process of the organic electronic device of this invention. It is a figure which shows sectional drawing which looked at the edge part of an example of the organic electronic device of this invention from the thickness direction.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits. The organic EL element in the present invention refers to an organic electroluminescence element. In this specification, (meth) acrylate is used in the meaning including both acrylate and methacrylate.

(Organic electronic devices)
The present invention relates to an organic electronic device including a glass substrate, an organic electronic element, and a barrier film. By using a barrier film having a function of blocking oxygen, moisture, nitrogen oxide, sulfur oxide, ozone, etc. in the atmosphere, the organic electronic element is sealed (sealed) with the barrier film and the glass substrate, thereby Organic electronic elements that can deteriorate over time even when used at room temperature and normal pressure due to oxygen and oxygen can be protected from deterioration. The organic electronic device of this invention has the structure adhere | attached on the said glass substrate so that the said organic electronic element may be sealed with the said glass substrate using the said barrier film. Such an organic electronic device generally has a structure including a portion including a glass substrate, an organic electronic element, and a barrier film in this order in the thickness direction of the substrate. The organic electronic device having the above structure includes, for example, (1) an organic electronic element is formed at the center of one surface of a glass substrate (in the present specification, the one surface of the glass substrate on which the organic electronic element is formed is referred to as “ (2) Apply an adhesive around the surface of the organic electronic device on the surface of the substrate obtained in (1); (3) Bond the barrier film to the substrate with the adhesive. Can be produced. That is, for example, an organic electronic element is formed in a rectangular shape at the center of the surface of the rectangular glass substrate, and then an adhesive is applied to completely surround the organic electronic element on the outside of the organic electronic element on the surface (for example, Finally, a barrier film can be adhered to the glass substrate with the adhesive from the surface side with respect to the glass substrate. In the present specification, the term “rectangular” means to include a square.

In the organic electronic device of the present invention, in the above structure, at least a part of the end of the barrier film is bonded to the glass substrate on the surface opposite to the front surface (sometimes referred to as “back surface” in this specification). This is one of the characteristics. That is, a barrier film is arrange | positioned from the surface to the back surface via the side surface (edge) which consists of glass substrate thickness, and adhere | attaches with a glass substrate in a back surface. By taking such a structure, a barrier film becomes a structure which covers at least one part of the edge part of a glass substrate, and the penetration | invasion of the external air from the covered edge part can be suppressed. The barrier film bonded to the glass substrate on the back surface may be further bonded to the glass substrate at the edge. Typically, at the end of the barrier film where the back surface is bonded to the glass substrate, the barrier film may be bonded to a part of the glass substrate edge and further bonded to the surface of the glass substrate end. .
The back surface of the glass substrate to which at least a part of the end portion of the barrier film is bonded may be at least the back surface of the end portion of the glass substrate.

  At least a part of the end of the barrier film may be any part, for example, a part corresponding to two opposing sides of the barrier film that is rectangular corresponding to the shape of the glass substrate. It may be all the end portions. When at least a part of the end of the barrier film is a part corresponding to two opposing sides in a rectangular barrier film, the part of the covered glass substrate also corresponds to two opposing sides in the rectangular glass substrate Any site may be used.

  In the present specification, the term “end” for a planar object such as a glass substrate and a barrier film means an outer peripheral portion within a specific distance from a side surface (edge) having a thickness. The distance is not particularly limited as long as it does not exceed the distance from the edge to the center of the plane, but may be, for example, 0.1 mm or more, 1 mm or more, 5 mm or more, 1 cm or more, 5 cm or more according to the size of the plane. 30 cm or less, 20 cm or less, 10 cm or less, 5 cm or less, and 1 cm or less. The specific distance may or may not be constant with respect to the outer periphery of one object.

(Barrier film)
The barrier film included in the organic electronic device of the present invention may be a barrier film having a barrier laminate including at least one organic layer and at least one inorganic layer on a substrate.
In the barrier film, the barrier laminate may be provided only on one side of the base film, or may be provided on both sides. The barrier laminate of the present invention may be laminated in the order of the inorganic layer and the organic layer from the base film side, or may be laminated in the order of the organic layer and the inorganic layer. The uppermost layer (the layer farthest from the substrate) to be laminated may be an inorganic layer or an organic layer, but is preferably an inorganic layer.

The barrier film may have a component other than the barrier laminate and the base material (for example, a functional layer such as an easy-adhesion layer). The functional layer may be placed on the barrier laminate, between the barrier laminate and the base film, or on the side where the barrier laminate on the base film is not placed (back side).
The barrier film is preferably transparent. An organic electronic device having a structure in which light passes from the organic electronic element to the organic electronic element through the barrier film (for example, a device having a structure in which light emission is extracted from the surface on which the barrier film is installed, or the barrier film side) It is particularly necessary for the solar cell having a light-receiving surface to be transparent.
The barrier film is preferably electrically insulating. In particular, it is preferable that individual constituent elements (for example, an inorganic layer, an organic layer, etc.) included in the barrier film are electrically insulating. For example, the barrier film used in the present invention is preferably not a barrier film containing a conductive metal foil.

(Barrier laminate)
The barrier laminate includes at least one organic layer and at least one inorganic layer, in which two or more organic layers and two or more inorganic layers are alternately laminated. Also good.
Further, the barrier laminate includes a so-called gradient material layer in which the organic region and the inorganic region continuously change in the film thickness direction in the composition constituting the barrier laminate in a range not departing from the gist of the present invention. Also good. As an example of the gradient material, a paper by Kim et al. “Journal of Vacuum Science and Technology A Vol. 23 p971-977 (2005 American Vacuum Society) Journal of Vacuum Science and Technology A Vol. 23, pages 971-977 (published in 2005) And a continuous layer in which the organic region and the inorganic region do not have an interface as disclosed in US Patent Publication No. 2004-46497. Hereinafter, for simplification, the organic layer and the organic region are described as “organic layer”, and the inorganic layer and the inorganic region are described as “inorganic layer”.

  Although there is no restriction | limiting in particular regarding the number of layers which comprise a barriering laminated body, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. Moreover, you may include other structural layers other than an organic layer and an inorganic layer.

(Organic layer)
The organic layer is preferably an organic layer containing an organic polymer as a main component. Here, the main component means that the first component of the component constituting the organic layer is an organic polymer, and usually 80% by weight or more of the component constituting the organic layer is an organic polymer.
Examples of the organic polymer include polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, and polyurethane. , Polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, thermoplastic resins such as acryloyl compound, or polysiloxane, etc. Examples thereof include organosilicon polymers. The organic layer may be made of a single material or a mixture, or may be a laminated structure of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as described above, as disclosed in US 2004-46497, the interface with the inorganic layer is not clear and the layer may be a layer whose composition changes continuously in the film thickness direction.

The organic layer in the present invention is preferably formed by curing a polymerizable composition containing a polymerizable compound.
(Polymerizable compound)
The polymerizable compound is preferably a radical polymerizable compound and / or a cationic polymerizable compound having an ether group as a functional group, more preferably a compound having an ethylenically unsaturated bond at the terminal or side chain, and / or A compound having an epoxy or oxetane at the terminal or side chain. Of these, compounds having an ethylenically unsaturated bond at the terminal or side chain are preferred. Examples of compounds having an ethylenically unsaturated bond at the terminal or side chain include (meth) acrylate compounds, acrylamide compounds, styrene compounds, maleic anhydride, etc., (meth) acrylate compounds and / or Styrenic compounds are preferred, and (meth) acrylate compounds are more preferred.

As the (meth) acrylate compound, (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and the like are preferable.
As the styrene compound, styrene, α-methylstyrene, 4-methylstyrene, divinylbenzene, 4-hydroxystyrene, 4-carboxystyrene and the like are preferable.

  Specific examples of the (meth) acrylate compound preferably used in the present invention are shown below, but the present invention is not limited to these.

Furthermore, a methacrylate compound represented by the following general formula (2) can also be preferably used.
General formula (2)

In general formula (2), R ¹¹ represents a substituent, which may be the same or different. n represents an integer of 0 to 5, and may be the same or different. However, at least one of R ¹¹ contains a polymerizable group.

As the substituent for R ¹¹ , —CR ¹² ₂ — (R ¹² is a hydrogen atom or a substituent), —CO—, —O—, a phenylene group, —S—, —C≡C—, —NR ¹³ — ( R ¹³ is a hydrogen atom or a substituent), —CR ¹⁴ ═CR ¹⁵ — (R ¹⁴ and R ¹⁵ are each a hydrogen atom or a substituent) and a combination of a polymerizable group. And a group comprising a combination of one or more of —CR ¹² ₂ — (R ¹² is a hydrogen atom or a substituent), —CO—, —O— and a phenylene group and a polymerizable group is preferable.

R ¹² is a hydrogen atom or a substituent, but is preferably a hydrogen atom or a hydroxy group.
It is preferable that at least one of R ¹¹ includes a hydroxy group. By containing a hydroxy group, the curing rate of the organic layer is improved.
The molecular weight of at least one R ¹¹ is preferably 10 to 250, more preferably 70 to 150.
The position where R ¹¹ is bonded is preferably bonded at least to the para position.
n represents an integer of 0 to 5, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 1.

In the compound represented by the general formula (2), it is preferable that at least two of R ¹¹ have the same structure. Furthermore, it is more preferable that n is 1 and at least two of each of four R ¹¹ have the same structure, and n is both 1, and the four R ¹¹ have the same structure. Is more preferable. The polymerizable group of the general formula (2) is preferably a (meth) acryloyl group or an epoxy group, and more preferably a (meth) acryloyl group. The number of polymerizable groups that the general formula (2) has is preferably 2 or more, and more preferably 3 or more. The upper limit is not particularly defined, but is preferably 8 or less, and more preferably 6 or less.
600-1400 are preferable and, as for the molecular weight of the compound represented by General formula (2), 800-1200 are more preferable.

Although the specific example of a compound represented by General formula (2) below is shown, this invention is not limited by this. Further, in the following compounds, the case where all four n's in the general formula (2) are 1 is exemplified, but one, two or three of the four n's in the general formula (2) are 0. A compound (for example, a bifunctional compound or a trifunctional compound), or one having two or more of the four n's in the general formula (2) (R ¹¹ is one ring, Those having two or more bonds, such as pentafunctional and hexafunctional compounds, are also exemplified as preferred compounds.

  The compound represented by the general formula (2) can be obtained as a commercial product. Moreover, the said compound is also compoundable by a well-known method. For example, epoxy acrylate can be obtained by reaction of an epoxy compound and acrylic acid. These compounds usually generate bifunctional, trifunctional, pentafunctional and isomers thereof during the reaction. When it is desired to separate these isomers, they can be separated by column chromatography, but in the present invention, they can also be used as a mixture.

The polymerizable compound is preferably contained in an amount of 90% by mass or more, more preferably 99% by mass or more, based on the solid content of the polymerizable composition.
Two or more kinds of polymerizable compounds may be contained in the composition for forming the organic layer.

(Silane coupling agent)
The polymerizable composition may contain a silane coupling agent. The silane coupling agent preferably contains a polymerizable group, and particularly preferably contains a (meth) acrylate group. Preferable silane coupling agents include silane coupling agents represented by the following general formula (1).

  In the formula, each R1 independently represents a hydrogen atom or a methyl group, R2 represents a halogen element or an alkyl group, R3 represents a hydrogen atom or an alkyl group, L represents a divalent linking group, and n represents 0. To an integer from 2 to 2.

Examples of the halogen element include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
1-12 are preferable, as for carbon number of the alkyl group in the substituent containing an alkyl group or an alkyl group among the below-mentioned substituents, 1-9 are more preferable, and 1-6 are more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group may be linear, branched or cyclic, but a linear alkyl group is preferred.

  The divalent linking group is preferably a linking group containing 1 to 20 carbons. Preferably it is a linking group containing 1 to 12, more preferably 1 to 6 carbons. Examples of the divalent linking group include an alkylene group (for example, ethylene group, 1,2-propylene group, 2,2-propylene group (also called 2,2-propylidene group, 1,1-dimethylmethylene group), 1,3-propylene group, 2,2-dimethyl-1,3-propylene group, 2-butyl-2-ethyl-1,3-propylene group, 1,6-hexylene group, 1,9-nonylene group, 1 , 12-dodecylene group, 1,16-hexadecylene group, etc.), arylene group (for example, phenylene group, naphthylene group), ether group, imino group, carbonyl group, sulfonyl group, and a plurality of these divalent groups in series. And divalent residues (for example, a polyethyleneoxyethylene group, a polypropyleneoxypropylene group, a 2,2-propylenephenylene group, etc.). These groups may have a substituent. Moreover, the connection group formed by couple | bonding two or more of these groups in series may be sufficient. Among these, an alkylene group, an arylene group, and a divalent group in which a plurality of these are bonded in series are preferable, and an unsubstituted alkylene group, an unsubstituted arylene group, and a divalent group in which these are bonded in series are more preferable. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, and an aryloxy group.

It is preferable that 1-30 mass% is contained with respect to solid content of a polymeric composition, and, as for a silane coupling agent, it is more preferable that 5-20 mass% is contained.
Moreover, in this invention, 2 or more types of silane coupling agents may be included, and those total amounts become the said range in this case.

  Although the specific example of a silane coupling agent is shown below, it is not limited to these.

  The proportion of the silane coupling agent in the solid content of the polymerizable composition (residue after the volatile component has volatilized) is preferably 1 to 20 mass%, more preferably 2 to 10 mass%.

(Polymerization initiator)
The polymerizable composition usually contains a polymerization initiator. When using a polymerization initiator, the content thereof is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol%, based on the total amount of compounds involved in the polymerization. By setting it as such a composition, the polymerization reaction via an active component production | generation reaction can be controlled appropriately. Examples of photopolymerization initiators include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819, etc.) and Darocur (Darocure) series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Esacure series (eg, Ezacure TZM, Ezacure TZT, Ezacure KTO 46, etc.) commercially available from Lamberti ), Ezacure KIP series and the like.

(solvent)
The polymerizable composition usually contains a solvent. Examples of the solvent include ketone and ester solvents, and 2-butanone, propylene glycol monoethyl ether acetate, and cyclohexanone are preferable. The content of the solvent is preferably 60 to 97% by mass of the polymerizable composition, and more preferably 70 to 95% by mass.

(Formation method of organic layer)
As a method of forming an organic layer from a polymerizable composition, it is applied to a plastic film, or a functional layer on a plastic film, or an inorganic layer, and then light (for example, ultraviolet rays), electron beam, or heat ray, The method of hardening is mention | raise | lifted.
Application methods include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, slide coating, or the hopper described in US Pat. No. 2,681,294. The extrusion coating method used can be adopted.
The organic layer may be formed by a vacuum film formation method such as flash vapor deposition.

The polymerizable composition is preferably cured by light. The light to irradiate is usually ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The radiation energy is preferably 0.1 J / cm ² or more, 0.5 J / cm ² or more is more preferable. When a (meth) acrylate compound is used as the polymerizable compound, the polymerization is inhibited by oxygen in the air, and therefore it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization. When the oxygen concentration during polymerization is lowered by the nitrogen substitution method, the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less. When the oxygen partial pressure during polymerization is reduced by the decompression method, the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm ² or more under a reduced pressure condition of 100 Pa or less.

  The organic layer is preferably smooth and has a high film hardness. The smoothness of the organic layer is preferably less than 1 nm as average roughness (Ra value) of 1 μm square, and more preferably less than 0.5 nm. The polymerization rate of the monomer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more. The polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

There is no particular limitation on the thickness of the organic layer. However, if it is too thin, it will be difficult to obtain film thickness uniformity. If it is too thick, cracks will be generated by external force and the barrier properties will be reduced. From this viewpoint, the film thickness of the organic layer is preferably 50 nm to 5000 nm, more preferably 200 nm to 4000 nm, and still more preferably 30 nm to 3000 nm.
The surface of the organic layer is required to be free of foreign matters such as particles and protrusions. For this reason, it is preferable that the organic layer is formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.
It is preferable that the organic layer has a high hardness. It has been found that when the hardness of the organic layer is high, the inorganic layer is formed smoothly and as a result, the barrier ability is improved. The hardness of the organic layer can be expressed as a microhardness based on the nanoindentation method. The microhardness of the organic layer is preferably 100 N / mm or more, and more preferably 150 N / mm or more.

(Inorganic layer)
The inorganic layer is a layer in the barrier laminate, and is usually a thin film layer made of a metal compound. As a method for forming the inorganic layer, any method can be used as long as it can form a target thin film. For example, there are physical vapor deposition methods (PVD) such as vapor deposition, sputtering and ion plating, various chemical vapor deposition methods (CVD), and liquid phase growth methods such as plating and sol-gel methods. The CVD method is preferred. The component contained in the inorganic layer is not particularly limited as long as it satisfies the above performance. For example, it is a metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide, and Si, Al, In An oxide, nitride, carbide, oxynitride or oxycarbide containing one or more metals selected from Sn, Zn, Ti, Cu, Ce and Ta can be preferably used. Among these, an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is preferable, an oxide or nitride of Si or Al is more preferable, and particularly silicon nitride (Si Nitride) is preferred. These may contain other elements as secondary components. For example, silicon nitride may be hydrogenated silicon nitride containing hydrogen, and may further be hydrogenated silicon oxynitride containing oxygen.

  As described above, in order to adhere the barrier film disposed on the surface of the glass substrate to the back surface of the glass substrate at the end, it is necessary to bend at least a part of the end of the barrier film. For example, a crack or the like may occur in the inorganic layer of the barrier film. When the inorganic layer contains silicon hydronitride, the inorganic layer becomes strong against tension, and similarly, the compression resistance tends to be improved. This tendency is presumed to be due to the formation of hydrogen bonds in the inorganic layer. The amount of hydrogen in the inorganic layer is preferably 25-30% atomic%. When the amount of hydrogen is larger than this, there is a possibility that the barrier property and oxidation resistance are lowered.

  The smoothness of the inorganic layer is preferably less than 1 nm as an average roughness (Ra value) of 1 μm square, and more preferably 0.5 nm or less. The inorganic layer is preferably formed in a clean room. The degree of cleanness is preferably class 10000 or less, more preferably class 1000 or less.

  One layer is usually in the range of 5 to 500 nm, preferably 10 to 200 nm. The film thickness of the inorganic layer may be larger than 20 nm, and may be 30 nm or more and 40 nm or more. The film thickness of the inorganic layer may be 100 nm or less, 50 nm or less, or 35 nm or less. The inorganic layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as described above, as disclosed in US 2004-46497, the interface with the organic layer is not clear and the layer may be a layer whose composition changes continuously in the film thickness direction.

(Formation method of inorganic layer)
The inorganic layer can be formed by a vacuum film forming method such as a sputtering method, a vacuum evaporation method, an ion plating method, or a plasma CVD method. When the inorganic layer is a layer containing silicon nitride, it is preferably formed by a plasma CVD method.

(Lamination of organic and inorganic layers)
The organic layer and the inorganic layer can be laminated by sequentially forming the organic layer and the inorganic layer in accordance with a desired layer structure.
In particular, when at least two organic layers and at least two inorganic layers are alternately laminated, high barrier properties can be exhibited. The alternate lamination may be carried out in the order of organic layer / inorganic layer / organic layer / inorganic layer from the support side, or may be laminated in the order of inorganic layer / organic layer / inorganic layer / organic layer.

(Functional layer)
The barrier laminate may have a functional layer. The functional layer is described in detail in paragraph numbers 0036 to 0038 of JP-A-2006-289627. Examples of functional layers other than these include matting agent layers, protective layers, solvent resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers. , Antifouling layer, printed layer, easy adhesion layer and the like.

(Base material)
The base material of the barrier film used in the organic electronic device of the present invention is preferably a plastic film. As long as the plastic film is a film that can hold the barrier laminate, the material, film thickness, and the like are not particularly limited, and can be appropriately selected according to the purpose of use. Depending on the type of organic electronic device, a transparent plastic film or a film with high optical properties may be preferred. Specifically, as a plastic film, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin , Cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin polymer, cycloolefin copolymer, fluorene ring modified polycarbonate resin, Examples thereof include thermoplastic resins such as alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds. The plastic film is preferably a polyester resin or a so-called optical film, the polyester resin is preferably polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), and the optical film is more preferably a cycloolefin polymer, a cycloolefin copolymer, or a polycarbonate resin.

  The thickness of the plastic film is not particularly limited, but is preferably thin. This is because, as a highly flexible barrier film, adhesion between the barrier film and the glass substrate on the back surface of the glass substrate is facilitated. If the substrate is thin, the distance of the inorganic layer from the bending center in the barrier film can be shortened, and the bending stress in the inorganic layer is reduced. The substrate may be usually 1 to 150 μm, more preferably 50 μm or less, and further preferably 25 μm or less.

(Glass substrate)
As the glass substrate in the organic electronic device of the present invention, any of the substrates used as the substrate of the organic electronic device may be used, and is not particularly limited.

The glass substrate may be chamfered. More specifically, in the glass substrate, the edges and the front surface, and the corners formed by the edge and the back surface may be chamfered. By using a chamfered glass substrate, stress on the barrier film formed so as to cover the edge portion can be relaxed, and adhesion between the barrier film and the glass substrate on the back surface of the glass substrate can be facilitated. . Although the form of chamfering is not particularly limited, it can be performed in an arc shape (R chamfering) or a polygonal shape. That is, the glass substrate can be formed so that the end portion of the glass substrate viewed from the thickness direction has an arc shape or a polygonal arc shape. The radius of curvature of the arc-shaped chamfer may be set, for example, from 1 cm to 0.1 mm according to the thickness of the glass substrate. For example, a radius of curvature of 0.2 mm or less can be used. Polygonal chamfering may have a minimum angle of preferably 120 degrees or more, more preferably 135 degrees or more, and even more preferably 150 degrees or more.
The chamfering method may be any method known to those skilled in the art. A commercially available glass substrate that has been chamfered may be used. Moreover, the chamfering should just be given at the edge of the crow board | substrate which is covered by adhering the edge part of a barrier film on the surface on the opposite side of a board | substrate at least.

(Bonding of a glass substrate on which an organic electronic element is formed and a barrier film)
The organic electronic device was formed by arranging the barrier film so as to sandwich the organic electronic device from above the surface of the glass substrate on which the organic electronic device is formed, and bonding the glass substrate and the barrier film. Bonding between the glass substrate and the barrier film may be performed. In order to allow at least a part of the end portion of the barrier film to adhere to the back surface of the glass substrate, there may be a portion in which the end portion of the barrier film is outside the end portion of the glass substrate. For example, when a rectangular (rectangular 1) barrier film and a rectangular (rectangular 2) glass substrate are combined, two sides parallel to the Y direction of the rectangular 1 and two sides parallel to the Y direction of the rectangular 2 are By arranging the two sides so that they are substantially parallel and the two sides parallel to the Y direction of the rectangle 1 are outside the two sides parallel to the Y direction of the rectangle 2 (see FIG. 1) Thus, it is possible to form a structure in which the barrier film is adhered on the back surface at the end portions located on the two sides.

  On the surface of the glass substrate on which the organic electronic element is formed, a barrier film may be provided by applying an adhesive to the outer periphery of the organic electronic element, and the barrier film may be used as a film for sealing by a solid sealing method. It may be used. The solid sealing method is a method in which a protective layer is preferably formed on a device, and then an adhesive layer and a barrier film are stacked and cured. However, the adhesive layer is preferably not provided on the organic electronic element. This is because the adhesive generally contains moisture.

Although there is no restriction | limiting in particular as an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.
Further, an adhesive sheet or a tape may be used. As the adhesive sheet, an adhesive sheet widely known as OCA (Optical Clear Adhesive) is exemplified.

  At the edge of the barrier film where the barrier film is bonded to the back surface of the glass substrate, an adhesive is applied in the direction passing through the outer peripheral portion of the organic electronic element on the surface, the edge of the glass substrate, the opposite surface, for example, The width may be 1 mm or more, 1 mm or more, 2 mm or more, 5 mm or more, or 1 cm or more. In order to reduce the influence of moisture on the element, the larger the width of the adhesive, the better. For example, depending on the size of the glass substrate and the purpose of use of the organic electronic device, 1 mm or less, 2 mm or less, 5 mm or less It may be provided with a width of about 1 cm or less or about 5 cm or less. At the end, the adhesive may be on the back surface only, on the back surface and the edge, or on the back surface, edge, and surface. For example, as shown in FIG. 2 (in FIG. 2, an example using a glass substrate chamfered in an arc shape is shown), the end of the barrier film is formed on the back surface, edge, and surface of the glass substrate. By providing the adhesive over the distance, it is possible to secure a distance (adhesive width) through which the outside air entering from the edge portion of the barrier film passes through the adhesive layer while suppressing the dead space of the organic electronic device.

When the barrier film has an end (non-bending end) other than the end (bending end) of the barrier film bonded to the back surface of the glass substrate, the width of the adhesive provided on the non-bending end is The width may be the same as or different from the width of the adhesive provided at the bent end. Generally, in order to seal the outside air as well, it is preferable that they are substantially the same. In this case, the width of the adhesive need only be achieved by the adhesive provided on the surface.
As can be seen from the above, since the space on the surface necessary for the adhesive can be suppressed at the bent end, the distance from the edge of the glass substrate to the organic electronic element is compared with the non-bent end. Can be shortened.

  When a barrier film provided with a barrier laminate on one side of the substrate is used, the barrier film may be adhered to the glass substrate so that the barrier laminate side is the organic electronic element side from the organic electronic element. preferable. Moreover, it is preferable that a barrier film is adhere | attached with a glass substrate so that the outermost surface layer of a barrier film may become an inorganic layer seeing from an organic electronic element. With the structure in which the outermost surface layer is an inorganic layer, it is possible to reduce moisture in a space including an organic electronic element constituted by a glass substrate and a barrier film.

(Organic electronic device)
As an example of the organic electronic element in the organic electronic device of the present invention, an element whose performance is deteriorated by a chemical component (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air is preferably exemplified. As an example of the said device, an organic EL element, a liquid crystal display element, a thin-film transistor, a touch panel, electronic paper, a solar cell etc. can be mentioned, for example, It is preferably used for an organic EL element.

Although it does not specifically limit as an organic EL element, The organic EL element of Unexamined-Japanese-Patent No. 2012-256904 can be used.
As the liquid crystal display element, the description in paragraph No. 0044 of JP2009-172993A can be referred to.
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper, solar cells described in Japanese Patent Application No. 7-160334, and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Preparation of barrier film]
Plasma treatment is performed on a smooth surface of polyethylene terephthalate (Toray, S10), and then 95 parts by weight of compound I represented by the following structural formula and 5 parts by weight of a polymerization initiator (Lamberti, Esacure KTO46). Is dissolved in 2-butanone solvent, coated to form a dry film thickness of 2000 nm, cured by irradiation with an ultraviolet ray irradiation amount of 0.5 J / cm ² in a nitrogen atmosphere with an oxygen content of 100 ppm or less, An organic layer was prepared. A first inorganic layer having a thickness of 40 nm was formed on the first organic layer by vacuum film formation. The first inorganic layer was formed by the composition shown in Table 1, silicon nitride (including oxygen and hydrogen in the film) was formed by plasma CVD, aluminum oxide was formed by sputtering, and silicon oxide was formed by vacuum evaporation. Further, a second organic layer was produced on the surface of the first inorganic layer in the same manner as the first organic layer. As shown in Table 1, in some examples, the second inorganic layer was formed on the surface of the second organic layer in the same manner as the first inorganic layer.

[Durability evaluation method]
We applied a method called the calcium corrosion method (see Asia Display / IDW'01 pp.1435-1438) to evaluate moisture ingress by fading of metallic calcium, and performed durability evaluation assuming actual organic electronic devices. .
Metal calcium is vapor-deposited on a glass substrate and sealed with a barrier film and an adhesive. An adhesive (Nagase ChemteX Corporation, XNR5516) was applied onto a glass substrate with a dispenser, bonded to a barrier film, and then cured by heating at + 80 ° C. for 1 hour at an ultraviolet irradiation amount of 6 J / cm ² . In the comparative example, the adhesive amount was adjusted so that the adhesive width was about 5 mm (adhesion of two sides parallel to the X direction) and 1 mm (adhesion of two sides parallel to the Y direction). In the examples, the ends of the barrier film arranged as shown in FIG. 1 that do not overlap with the glass substrate on the two sides parallel to the Y direction are bent to form the two ends on the glass substrate parallel to the Y direction. Wrapped and bonded with an adhesive width of 1mm on the front surface and 4mm on the back surface, the two sides parallel to the X direction of the barrier film were bonded to the edge of the two sides parallel to the X direction of the glass substrate with an adhesive width of 5mm surface .

After the sealed sample is stored in a high-temperature and high-humidity tank at 60 ° C / 90% for 1000 hours, the fading rate is measured from the fading area of metallic calcium and the original calcium area, and the durability shown in Table 2 is used. evaluated. The results are shown in Table 1.
In the description of the end structure in Table 1, “right angle indicates no chamfering, R indicates a circular chamfer (curvature radius of 0.2 mm), and C indicates a polygonal chamfer (inner angle of 135 degrees). A certain amount of H was determined from the atomic ratio by measuring the number of elements and atoms in the inorganic layer by Rutherford backscattering and hydrogen forward scattering analysis.

1. 1. Glass substrate 2. Organic electronic device 3. Barrier film adhesive

Claims (17)

A glass substrate, an organic electronic device formed on the surface of the glass substrate, and a barrier film adhered to the glass substrate, wherein the barrier film seals the organic electronic device together with the glass substrate. An organic electronic device bonded to a glass substrate,
The barrier film includes a substrate, at least one organic layer, at least one inorganic layer,
An organic electronic device in which at least a part of an end of the barrier film is bonded to the glass substrate on the back surface of the glass substrate. The organic electronic device according to claim 1, wherein at least a part of the end portion of the barrier film is bonded to the glass substrate at a back surface and a front surface of the glass substrate. The organic electronic device according to claim 1, wherein the thickness of the base material is 50 μm or less. The organic electronic device according to claim 1, wherein the thickness of the base material is 25 μm or less. The organic electronic device according to claim 1, wherein the inorganic layer is made of a silicon compound or an aluminum compound. The organic electronic device according to claim 5, wherein the inorganic layer includes one or more selected from the group consisting of silicon nitride, hydrogenated silicon nitride, and hydrogenated silicon oxynitride. The organic electronic device according to claim 1, wherein the inorganic layer contains hydrogen of 25% atom or more and 30% atom or less. The organic electronic device according to claim 1, wherein the outermost surface layer on the glass substrate side of the barrier film is an inorganic layer. The organic electronic device according to any one of claims 1 to 8, wherein an end of the glass substrate bonded to the barrier film on the back surface is chamfered. The organic electronic device according to claim 9, wherein an end of the glass substrate bonded to the barrier film on the back surface has an arc shape. The organic electronic device according to claim 10, wherein a radius of curvature of the arc is 0.2 mm or less. The organic electronic device according to claim 9, wherein an end portion of the glass substrate bonded to the barrier film on the back surface has a polygonal shape. The organic electronic device according to claim 12, wherein a minimum angle of the polygon is 135 degrees or more. The organic electronic device according to claim 1, wherein the organic electronic element is an organic EL element. The barrier film has a rectangular shape 1;
The ends of the barrier film on two sides parallel to the Y direction of the rectangle 1 are bonded to the glass substrate on the back surface, and the glass substrate has a shape of the rectangle 2, and the barrier film is bonded. The organic electronic device as described in any one of Claims 1-14 which exists in the edge part of 2 sides of the back surface which is parallel to the Y direction of the rectangle 2. The organic electronic device according to claim 15, wherein an end portion of the barrier film is not bonded to the glass substrate on the back surface at two sides parallel to the X direction of the rectangle 1. The distance from the edge of the glass substrate to the organic electronic element at two sides parallel to the Y direction of the rectangle 2 to the organic electronic element from the edge of the glass substrate at two sides parallel to the X direction of the rectangle 2 The organic electronic device according to claim 15 or 16, wherein the organic electronic device is shorter than the distance up to.

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