JP5161470B2 - GAS BARRIER LAMINATED FILM, PROCESS FOR PRODUCING THE SAME, AND IMAGE DISPLAY ELEMENT - Google Patents

Description

  The present invention relates to a gas barrier laminate film having excellent gas barrier performance and a method for producing the same. More particularly, the present invention relates to a gas barrier laminate film that can be suitably used for various image display elements, and particularly useful as a substrate for flexible organic electroluminescence elements (hereinafter referred to as “organic EL elements”). The present invention relates to a laminated film, a manufacturing method thereof, and an organic EL element.

  Conventionally, a gas barrier laminate film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging articles that require blocking of various gases such as water vapor and oxygen, It is widely used in packaging applications to prevent the deterioration of food, industrial goods and pharmaceuticals. Recently, gas barrier laminate films are being used in liquid crystal display elements, solar cells, EL, and the like in addition to packaging applications.

  In the development process of image display elements such as liquid crystal display elements and EL elements in recent years, long-term reliability and flexibility of shape are required for transparent base materials forming these elements in addition to the conditions of weight reduction and size increase. Advanced conditions such as high image quality and the ability to display curved surfaces are also required. As a transparent base material satisfying such advanced conditions, a plastic base material has begun to be adopted as a new base material that replaces a conventional glass substrate that is heavy, fragile and difficult to increase in area. In the case of a plastic substrate, not only the above conditions are satisfied, but it is possible to manufacture by a roll-to-roll method, so that the productivity is better than a glass substrate and it is advantageous in terms of cost reduction.

However, film substrates such as transparent plastics have the disadvantage that the gas barrier performance is inferior to that of glass substrates. If a base material with inferior gas barrier properties is used, water vapor or air will permeate, causing deterioration of the liquid crystal in the liquid crystal cell, for example, resulting in display defects and deterioration of display quality. In order to solve such a problem, a gas barrier laminate film in which a metal oxide thin film is formed on a base film has been developed so far. For example, as gas barrier laminated films used for packaging materials and liquid crystal display elements, those obtained by depositing silicon oxide on a plastic film (Patent Document 1) and those obtained by depositing aluminum oxide (Patent Document 2) are known. Both have a water vapor barrier property of about 1 g / (m ² · day).

On the other hand, in large-sized liquid crystal displays and high-definition displays that have been developed in recent years, the gas barrier performance required for plastic film substrates is about 0.1 g / (m ² · day) in terms of water vapor barrier properties. Furthermore, recently, the development of organic EL displays, high-definition color liquid crystal displays, etc. has progressed, and while maintaining the transparency that can be used in these displays, it has a higher barrier performance, particularly 0.1 g / (m ² · day for a water vapor barrier. There is a need for transparent substrates with performance below.
In order to meet these demands, recently, as a means for expecting higher barrier performance, film formation by sputtering method or CVD method in which a thin film is formed using plasma generated by glow discharge under low pressure conditions has been studied. ing. In addition, an organic light emitting device in which a barrier film having an alternately laminated structure of organic layers / inorganic layers is produced by a vacuum deposition method has been proposed (Patent Document 3). However, since this device has insufficient bending resistance, it cannot be applied to a flexible image display element.

In order to provide the bending resistance necessary for application to a flexible image display element, a technique is disclosed in which a polymer obtained by polymerizing an acrylic monomer having a volume shrinkage rate of less than 10% is used in an organic layer (Patent Literature). 4). However, this technique has a problem that the gas barrier property is not sufficient.
Therefore, it has been desired to develop a plastic film having gas barrier properties and bending resistance that can be applied to flexible image display elements.
Japanese Examined Patent Publication No. 53-12953 (Example) JP 58-217344 A (Example) US Pat. No. 6,268,695 (page 4 [2-5] to page 5 [4-49]) JP 2003-53881 A (Page 3 [0006] to Page 4 [0008])

  This invention is made | formed in view of the said subject, and the 1st objective of this invention is to provide the gas-barrier laminated | multilayer film which can maintain the gas-barrier property outstanding even if it bends. A second object of the present invention is to provide an image display element having excellent durability using the gas barrier laminate film.

  As a result of earnestly examining the cause of the problems of the prior art, the present inventor is partly due to insufficient adhesion between the inorganic layer and the organic layer formed on the base film. I found. Then, as a result of examining increasing the gas barrier property and the bending resistance while sufficiently ensuring the adhesion between the inorganic layer and the organic layer, the present invention described below has been provided.

[1] A method for producing a gas barrier laminate film having at least one inorganic layer and at least one organic layer on a substrate film, wherein an acrylate monomer having a phosphate ester group and a phosphate ester group are produced. A method for producing a gas barrier laminate film comprising the step of forming the organic layer by polymerizing a monomer composition containing a methacrylate monomer or a mixture thereof.
[2] The gas barrier laminate film according to [1], wherein the acrylate monomer having a phosphate ester group and the methacrylate monomer having a phosphate ester group are represented by the following general formula (1): Production method.

［一般式（１）において、Ｚ¹はＡｃ²−Ｏ−Ｘ²−、重合性基を有しない置換基または水素原子を表し、Ｚ²はＡｃ³−Ｏ−Ｘ³−、重合性基を有しない置換基または水素原子を表し、Ａｃ¹、Ａｃ²およびＡｃ³は各々独立にアクリロイル基またはメタクリロイル基を表し、Ｘ¹、Ｘ²およびＸ³は各々独立にアルキレン基、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基、またはこれらの組み合わせを表す。］
［３］ 前記モノマー組成物が前記一般式（１）で表されるモノマーを１〜５０質量％含むことを特徴とする［１］または［２］に記載のガスバリア性積層フィルムの製造方法。
［４］ 前記モノマー組成物が、２官能アクリレートモノマー、２官能メタクリレートモノマー、またはこれらの混合物を含むことを特徴とする［１］〜［３］のいずれか一項に記載のガスバリア性積層フィルムの製造方法。
［５］ 前記有機層をフラッシュ蒸着で製膜し、かつ、１００Ｐａ以下の真空中で前記モノマー組成物を重合することを特徴とする［１］〜［４］のいずれか一項に記載のガスバリア性積層フィルムの製造方法。
［６］ 常に１００Ｐａ以下の真空中で前記有機層と前記無機層を積層することを特徴とする［１］〜［５］のいずれか一項に記載のガスバリア性積層フィルムの製造方法。

[In General Formula (1), Z ¹ represents Ac ² —O—X ² —, a substituent having no polymerizable group or a hydrogen atom, Z ² represents Ac ³ —O—X ³ —, a polymerizable group. Each having no substituent or hydrogen atom, each of Ac ¹ , Ac ² and Ac ³ independently represents an acryloyl group or a methacryloyl group, and X ¹ , X ² and X ³ are each independently an alkylene group, an alkyleneoxy group, an alkylene An oxycarbonyl group, an alkylenecarbonyloxy group, or a combination thereof is represented. ]
[3] The method for producing a gas barrier laminated film according to [1] or [2], wherein the monomer composition contains 1 to 50% by mass of the monomer represented by the general formula (1).
[4] The gas barrier laminate film according to any one of [1] to [3], wherein the monomer composition includes a bifunctional acrylate monomer, a bifunctional methacrylate monomer, or a mixture thereof. Production method.
[5] The gas barrier according to any one of [1] to [4], wherein the organic layer is formed by flash vapor deposition, and the monomer composition is polymerized in a vacuum of 100 Pa or less. For producing a conductive laminated film.
[6] The method for producing a gas barrier laminate film according to any one of [1] to [5], wherein the organic layer and the inorganic layer are always laminated in a vacuum of 100 Pa or less.

[7] A gas barrier laminate film produced by the production method according to any one of [1] to [6].

[8] A gas barrier laminate film having at least one inorganic layer and at least one organic layer on a base film, wherein the organic layer includes a polymer having at least one phosphate group. A gas barrier laminate film characterized in that

[9] The gas barrier laminate film according to [7] or [8], wherein the organic layer and the inorganic layer are laminated on the base film in this order.
[10] The gas barrier laminate according to any one of [7] to [9], which has a structure in which the inorganic layer and the organic layer are laminated in this order on the base film. the film.
[11] The gas barrier property according to any one of [7] to [10], wherein each of the base film has at least one inorganic layer and at least one organic layer on both surfaces. Laminated film.
[12] The gas barrier laminate film according to any one of [7] to [11], further having a transparent conductive layer.
[13] Oxygen permeability at 38 ° C. and 90% relative humidity is 0.02 ml / (m ² · day · atm) or less, and water vapor permeability at 38 ° C. and 90% relative humidity is 0.01 g / (m The gas barrier laminate film according to any one of [7] to [12], which is ² · day) or less.

[14] An image display device using the gas barrier laminate film according to any one of [7] to [13].
[15] The image display element according to [14], wherein the image display element is flexible.
[16] The image display device according to [14] or [15], wherein the image display device is an organic EL device.

  The gas barrier laminate film of the present invention has high gas barrier performance and excellent bending resistance. Moreover, the image display element of the present invention having the gas barrier laminate film having such characteristics has high durability.

  Hereinafter, the gas barrier laminate film and the image display element of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Gas barrier laminate film]
(Layer structure)
The gas barrier laminate film of the present invention has at least one inorganic layer and at least one organic layer on the base film. If it has an inorganic layer and an organic layer on a base film, each layer number and lamination | stacking order will not be restrict | limited. For example, it may be formed on the base film in the order of the inorganic layer and the organic layer, or may be formed on the base film in the order of the organic layer and the inorganic layer. Preferred is one in which inorganic layers and organic layers are alternately formed. For example, what was formed in order of the inorganic layer, the organic layer, and the inorganic layer on the base film can be mentioned as a preferable example. The number of inorganic layers and organic layers is preferably 1 to 10 layers, more preferably 1 to 5 layers, and even more preferably 1 to 3 layers. The inorganic layer and the organic layer may be formed only on one side of the base film, or may be formed on both sides.

  Moreover, the functional layer may be formed between the base film and the inorganic layer, between the base film and the organic layer, and between the inorganic layer and the organic layer. Examples of functional layers include optical functional layers such as antireflection layers, polarizing layers, color filters, and light extraction efficiency improving layers; mechanical functional layers such as hard coat layers and stress relaxation layers; antistatic layers and conductive layers An electric functional layer; an antifogging layer; an antifouling layer; a printing layer and the like.

A gas barrier in which at least an inorganic layer, an organic layer, and an inorganic layer are laminated in this order on the substrate film surface (opposite surface) opposite to the side having the inorganic layer and the organic layer containing a polymer having a phosphate group. A conductive laminate layer can be provided. By providing such a gas barrier laminate layer, water molecules can be prevented from entering from the opposite surface. As a result, the dimensional change of the gas barrier laminate film can be suppressed to prevent stress concentration and destruction on the inorganic layer, and as a result, durability can be further enhanced.
Below, each layer which comprises the gas barrier laminated film of this invention is demonstrated in detail.

(Organic layer)
The organic layer constituting the gas barrier laminate film of the present invention is characterized by containing a polymer having a phosphate group. The polymer having a phosphate ester group can be produced by polymerizing a monomer composition containing a polymerizable monomer having a phosphate ester group.

  As the monomer having a phosphoric ester group used in the present invention, a compound represented by the following general formula (1) can be preferably used.

In the general formula (1), Z ¹ represents Ac ² —O—X ² —, a substituent having no polymerizable group or a hydrogen atom, and Z ² represents Ac ³ —O—X ³ —, which has a polymerizable group. And Ac ¹ , Ac ² and Ac ³ each independently represents an acryloyl group or a methacryloyl group, and X ¹ , X ² and X ³ each independently represent an alkylene group, an alkyleneoxy group, an alkyleneoxy group A carbonyl group, an alkylenecarbonyloxy group, or a combination thereof is represented.

  The general formula (1) is represented by a monofunctional monomer represented by the following general formula (2), a bifunctional monomer represented by the following general formula (3), and the following general formula (4). Trifunctional monomers are included.

The definitions of Ac ¹ , Ac ² , Ac ³ , X ¹ , X ² and X ³ are the same as those in the general formula (1). In the general formulas (2) and (3), R ¹ represents a substituent or a hydrogen atom having no polymerizable group, and R ² represents a substituent or a hydrogen atom having no polymerizable group.

In the general formula (1) ~ (4), X 1, the number of carbon atoms of X ² and X ³ is preferably 1 to 12, more preferably 1 to 6, 1 to 4 is more preferred. Specific examples of the alkylene group X ^1, X ² and X ³ may take, and, X ^1, alkyleneoxy groups X ² and X ³ can take an alkyleneoxy carbonyl group, specific examples of the alkylene moiety of the alkylene carbonyloxy group Includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. The alkylene group may be linear or branched, but is preferably a linear alkylene group. X ¹ , X ² and X ³ are preferably an alkylene group.

In the general formulas (1) to (4), examples of the substituent having no polymerizable group include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a group obtained by combining these. Preferred are an alkyl group and an alkoxy group, and more preferred is an alkoxy group.
1-12 are preferable, as for carbon number of an alkyl group, 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 is preferably a linear alkyl group. The alkyl group may be substituted with an alkoxy group, an aryl group, an aryloxy group, or the like.
6-14 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group may be substituted with an alkyl group, an alkoxy group, an aryloxy group, or the like.
For the alkyl part of the alkoxy group and the aryl part of the aryloxy group, the description of the alkyl group and the aryl group can be referred to.

  In the present invention, only one type of monomer represented by the general formula (1) may be used, or two or more types may be used in combination. When used in combination, the monofunctional monomer represented by the general formula (2), the bifunctional monomer represented by the general formula (3), and the trifunctional monomer represented by the general formula (4) Two or more kinds may be used in combination.

In the present invention, commercially available compounds such as the KAYAMER series manufactured by Nippon Kayaku Co., Ltd. and the Phosmer series manufactured by Unichemical Co., Ltd. may be used as they are as the polymerizable monomers having a phosphate ester group. Well, newly synthesized compounds may be used.
Specific examples of the polymerizable monomer having a phosphate ester group are shown below, but the monomer that can be used in the present invention is not limited thereto.

  The monomer composition used in the present invention contains a polymerizable monomer having no phosphate ester group in addition to the polymerizable monomer having a phosphate ester group represented by the general formula (1). Is preferred. As such a monomer, an acrylate monomer having no phosphate ester group or a methacrylate monomer having no phosphate ester group can be preferably exemplified. These acrylate monomers and methacrylate monomers may be monofunctional or bifunctional or more. Preferred is a case where the monomer composition contains a bifunctional acrylate monomer or a bifunctional methacrylate monomer represented by the following general formula (5), and these are contained in the monomer composition in an amount of 50 to 99% by mass. It is preferable.

In General Formula (5), Ac ¹¹ and Ac ¹² each independently represent an acryloyl group or a methacryloyl group, L is a carbon number of 8 or more, and does not contain an oxygen atom, a nitrogen atom, or a sulfur atom in the chain Represents an alkylene group. Carbon number of L becomes like this. Preferably it is 8-19, More preferably, it is 8-14, More preferably, it is 8-12. The alkylene group constituting L may be substituted or unsubstituted. Examples of the substituent for the alkylene group include an alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 2-4.
Specific examples of the bifunctional monomer represented by the general formula (5) are shown below, but the bifunctional monomer that can be used in the present invention is not limited to these.

  In the monomer composition used in the present invention, only one type of polymerizable monomer having no phosphate group may be used, or two or more types may be used in combination. The monomer composition used in the present invention preferably contains 1 to 50% by mass of a monomer having a phosphate ester group, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass. If the content rate of a phosphate ester monomer is 1-50 mass%, it will be easy to improve the adhesiveness and gas barrier property between inorganic layers.

  Examples of the method for forming the organic layer include a coating method and a vacuum film forming method. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, Examples thereof include a slide coating method, a spray coating method, and an extrusion coating method using a hopper described in US Pat. No. 2,681,294. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. Although there is no restriction | limiting in particular as a vacuum film-forming method, Flash vapor deposition as described in each specification, such as US Patent 4,842,893, 4,954,371, 5,032,461, etc. The method is preferred.

  The monomer polymerization method is not particularly limited, but heat polymerization and active energy ray polymerization are preferably used. Among these, active energy ray polymerization is particularly preferable in that it can be easily attached in a vacuum chamber and a high molecular weight can be rapidly obtained by a crosslinking reaction. The active energy ray means radiation capable of propagating energy by irradiation with ultraviolet rays, X-rays, electron beams, infrared rays, microwaves, etc., and the type and energy thereof can be arbitrarily selected according to the application. .

  When carrying out photopolymerization, a photopolymerization initiator is used in combination. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959 Irgacure 907, Irgacure 369, commercially available from Ciba Specialty Chemicals. , Irgacure 379, Irgacure 819, etc.), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Sartomer) Ezacure TZM, ezacure TZT, etc.). The polymerization of the monomer is preferably performed after the monomer composition is disposed on the base film.

The irradiation light is usually preferably ultraviolet light from a high pressure mercury lamp or a low pressure mercury lamp. The irradiation energy is preferably 0.5 J / cm ² or more, and more preferably ² J / cm ² or more. Since acrylate and methacrylate are subject to polymerization inhibition by oxygen in the air, it is preferable to lower 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 ² J / cm ² or more under a reduced pressure condition of 100 Pa or less.

  You may mix the polymer which does not have a structural unit represented by General formula (1) with an organic layer. Examples of such polymers are polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, polyetherether. Examples include ketones, polycarbonates, alicyclic polyolefins, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and fluorene ring-modified polyester. The content of the polymer having no structural unit represented by the general formula (1) in the organic layer is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and 5 to 10%. More preferably, it is mass%.

  The thickness of the organic layer containing the polymer having a phosphate ester group is not particularly limited, but is preferably 10 nm to 5 μm, more preferably 10 nm to 2 μm, and still more preferably 10 nm to 1 μm.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. The component contained in the inorganic layer is not particularly limited. For example, an oxide or nitride containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, Zr, Ta, and the like Alternatively, oxynitride or the like can be used. Among these, a metal oxide, nitride or oxynitride selected from Si, Al, In, Sn, Zn, Zr and Ti is preferable, and a metal oxide selected from Si, Al, Sn, Zr and Ti. Nitride or oxynitride is more preferable. Moreover, the inorganic layer which consists of these composites is also preferable. In addition to these, other elements may be contained as secondary components.

  The inorganic layer can be formed by vapor deposition, physical vapor deposition (PVD) such as sputtering or ion plating, various chemical vapor deposition (CVD), or liquid phase such as plating or sol-gel. There is a growth method. Among these, chemical vapor deposition (CVD) and physical vapor deposition are effective in avoiding the effects of heat on the base film during inorganic layer formation, high production speed, and easy to obtain a uniform thin film layer. The method (PVD) is preferred. Moreover, it is also preferable to form an inorganic layer by a sol-gel method from the viewpoint that a thick film can be easily obtained. Here, the thick film refers to a film in the range of 100 nm to 1 μm.

  The thickness of the inorganic layer is preferably 30 nm to 1 μm, and more preferably 50 to 200 nm. When the thickness of the inorganic layer is in the range of 50 nm to 1 μm, it is difficult to be affected by defective portions and portions having low density between crystals, and high gas barrier properties are obtained. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.

(Base film)
The base film used for the gas barrier laminate film of the present invention is preferably selected from those made of a heat-resistant material so that it can be used as an image display element described later. A preferable base film is a transparent plastic film having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance. Tg and the linear expansion coefficient can be changed by an additive or the like.

  The polymer used for the base film may be either a thermoplastic polymer or a thermosetting polymer. The thermoplastic polymer preferably has a polymer Tg of 130 to 300 ° C, more preferably 160 to 250 ° C. Further, in order to achieve optical uniformity, an amorphous polymer is preferable. Examples of such thermoplastic resins include the following (in parentheses indicate Tg).

  Polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of JP 2001-150584 A: 162 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modification Polycarbonate (IP-PC: compound of JP 2000-227603 A: 205 ° C.), acryloyl compound (compound of JP 2002-80616 A: 300 ° C. or higher). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  Examples of the thermosetting polymer include epoxy resins and radiation curable resins. Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among them, from the viewpoints of solvent resistance, optical properties, thermal properties, etc., acid anhydrides and polymers containing acid anhydride structures or aliphatic amines are preferably used, and acid anhydrides and acid anhydride structures are particularly preferred. It is a polymer containing. Furthermore, it is preferable to add an appropriate amount of a known curing catalyst such as tertiary amines and imidazoles.

  A radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, an unsaturated double molecule such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. A resin containing a bond. Among these, an acrylic resin containing an acryloyl group is particularly preferable. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but an acrylic resin having two or more acryloyl groups in a molecule or unit structure may be used. preferable. Examples of such polyfunctional acrylate resins include urethane acrylates, ester acrylates, and epoxy acrylates, but those that can be used in the present invention are not limited to these.

  In the case of using an ultraviolet curing method, an appropriate amount of a known photoreaction initiator is added to these radiation curable resins.

  In order to further strengthen the interaction with the polymer molecule, an alkoxysilane hydrolyzate or a silane coupling agent may be mixed with the epoxy resin and the radiation curable resin. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, or an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, or a mercapto group. Preferably, in this case, those having a vinyl group having the same reactive group are particularly preferably used for fixing to the main component resin. For example, KBM-503, KBM-803 of Shin-Etsu Chemical Co., Ltd., Nippon Unicar Co., Ltd. A-187 made by) or the like is used. These addition amounts are preferably 0.2 to 3% by mass.

  When the gas barrier laminate film of the present invention is used as an image display element such as a display, a transparent substrate film, that is, a light transmittance of 80% or more, preferably 85% or more, more preferably 90% or more. It is preferable to use a certain base film. If the light transmittance of the base film is 80% or more, it can be suitably used as a base film of an organic EL element described later.

  It goes without saying that an opaque material can be used for applications that do not necessarily require transparency, such as when not used on the viewing side even when used for display applications, or for opaque packaging materials. Examples thereof include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The light transmittance used as a scale of transparency in this specification is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device. It can be calculated by subtracting the diffuse transmittance from the light transmittance.

(Transparent conductive layer)
A transparent conductive layer can be laminated on at least one side of the laminated film of the present invention. A known metal film, metal oxide film, or the like can be applied as the transparent conductive layer. Among these, a metal oxide film having excellent transparency, conductivity, and mechanical properties is preferably used as the transparent conductive layer. The metal oxide film is, for example, a metal oxide film of indium oxide, cadmium oxide or tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium or the like is added as an impurity; an oxide to which aluminum is added as an impurity Examples thereof include metal oxide films such as zinc and titanium oxide. Among them, an indium oxide thin film mainly composed of tin oxide and containing 2 to 15% by mass of zinc oxide is excellent in transparency and conductivity, and is preferably used.

  The transparent conductive layer can be formed by any method as long as it can form a target thin film. For example, a vapor deposition method that forms a film by depositing a material from the vapor phase, such as sputtering, vacuum deposition, ion plating, plasma CVD, and Cat-CVD, is suitable. The film can be formed by the methods described in Japanese Patent Laid-Open Nos. 2002-322561 and 2002-361774. Among these, the sputtering method is preferable from the viewpoint that particularly excellent conductivity and transparency can be obtained.

  The preferred degree of vacuum of the sputtering method, vacuum deposition method, ion plating method, or plasma CVD method is 0.133 mPa to 6.65 Pa, preferably 0.665 mPa to 1.33 Pa. Before forming the transparent conductive layer, it is preferable to subject the base film to a surface treatment such as plasma treatment (reverse sputtering) or corona treatment. Moreover, you may heat up to 50-200 degreeC during providing the transparent conductive layer.

  The film thickness of the transparent conductive layer thus obtained is preferably 20 to 500 nm, and more preferably 50 to 300 nm.

  The surface electrical resistance of the transparent conductive layer measured at 25 ° C. and 60% relative humidity is preferably 0.1 to 200Ω / □, and more preferably 0.1 to 100Ω / □. More preferably, it is 0.5-60Ω / □. Moreover, the light transmittance of the transparent conductive layer is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more.

(Characteristics and utilization of gas barrier laminate film)
The gas barrier laminate film of the present invention has low oxygen permeability and water vapor permeability, and exhibits excellent gas barrier properties. Specifically, it is possible to provide a laminated film having an oxygen transmission rate of 0.01 ml / (m ² · day · atm) or less at 38 ° C. and 10% relative humidity. Further, it is possible to provide a laminated film having an oxygen permeability of 0.02 ml / (m ² · day · atm) or less at 38 ° C. and a relative humidity of 90%, preferably 0.01 ml / (m ² · day). -Atm) It is possible to provide the following laminated films. Furthermore, it is possible to provide a laminated film having a water vapor transmission rate of 0.01 g / (m ² · day) or less at 38 ° C. and a relative humidity of 90%. Further, such excellent gas barrier properties of the present invention are maintained even after the laminated film is bent a plurality of times. Furthermore, the laminated film of the present invention has a feature that adhesion between the inorganic layer and the organic layer is high.
Because of such advantageous characteristics, the gas barrier laminate film of the present invention can be effectively applied to a wide variety of articles and flexible articles that are required to block water vapor, oxygen, and the like. sell. For example, food packaging film, industrial product packaging film, pharmaceutical packaging film, flexible display substrate film, flat panel display substrate film, solar cell substrate film, touch panel substrate film, flexible circuit substrate film, optical disc protection It can be used for films, optical films, retardation films, polarizing plate protective films, transparent conductive films and the like.

[Image display element]
In particular, the gas barrier laminate film of the present invention can be effectively used for an image display element. Here, the image display element refers to all elements having an image display function such as a circularly polarizing plate, a liquid crystal display element, an organic EL element, and electronic paper. In these image display elements, the gas barrier laminate film of the present invention can be suitably used as a substrate or a sealing film. Since the gas barrier laminate film of the present invention has excellent bending resistance, its characteristics can be effectively used when used in a flexible image display element. The term “flexible” as used herein means that the portion to which the gas barrier laminate film is applied is not fixed and has a function capable of changing the shape depending on the use mode.
Below, the circularly-polarizing plate, liquid crystal display element, and organic EL element which can use the gas barrier laminated film of this invention preferably are demonstrated in order.

(Circularly polarizing plate)
The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier laminate film of the present invention. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

(Liquid crystal display element)
Liquid crystal display devices can be broadly classified into reflective liquid crystal display devices and transmissive liquid crystal display devices.
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier laminate film of the present invention can be used as a transparent electrode and an upper substrate. When the reflective liquid crystal display device has a color display function, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization, in that order from the bottom. It has a structure consisting of a film. Among these, the gas barrier laminate film of the present invention can be used as an upper transparent electrode and an upper substrate. Further, when the transmissive liquid crystal display device is provided with a color display function, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The structure of the liquid crystal layer is not particularly limited. For example, a TN (Twisted Nematic) type, STN (Super Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertical Alignment) type, ECB (Electrically Controlled Birefringence) type, An OCB (Optically Compensated Bend) type or a CPA (Continuous Pinwheel Alignment) type is preferable.

[Organic EL device]
The gas barrier laminate film of the present invention can be particularly preferably used for an organic EL device. An organic EL element has a cathode and an anode on a substrate, and has an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
As an aspect of lamination of the organic compound layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

(anode)
The anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene and polypyrrole Organic conductive materials, and laminates of these with ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic EL device of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting device, but is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof. The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method. The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more. The transparent anode is described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

(cathode)
The cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Say. The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like. Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode formation position is not particularly limited, and may be formed on the entire organic compound layer or a part thereof. A dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like. The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

(Organic compound layer)
The organic compound layer in the present invention will be described.
The organic EL device of the present invention has at least one organic compound layer including a light emitting layer, and as the organic compound layer other than the organic light emitting layer, as described above, a hole transport layer, an electron transport layer, Examples include a charge blocking layer, a hole injection layer, and an electron injection layer.
In the organic EL device of the present invention, each layer constituting the organic compound layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

(1) Organic light-emitting layer The organic light-emitting layer receives holes from the anode, hole injection layer, or hole transport layer and receives electrons from the cathode, electron injection layer, or electron transport layer when an electric field is applied. And a layer having a function of emitting light by providing a recombination field of electrons. The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and pyromethene derivatives And various metal complexes typified by metal complex, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

  Examples of the phosphorescent material that can be used in the present invention include a complex containing a transition metal atom or a lanthanoid atom. Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum. Examples of lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

  Examples of the ligand of the complex include G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, “Photochemistry and Photophysics of Coordination Compounds”, Springer-Verlag, 1987, Akio Yamamoto. Examples of the ligands described in the book “Organic Metal Chemistry-Fundamentals and Applications-” published in 1982 by Hankabosha. Specific ligands are preferably halogen ligands (preferably chlorine ligands), nitrogen-containing heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, phenanthroline, etc.), diketones Ligand (for example, acetylacetone), carboxylic acid ligand (for example, acetic acid ligand), carbon monoxide ligand, isonitrile ligand, cyano ligand, more preferably nitrogen-containing Heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass. Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later. Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is further more preferable that they are 10 nm-100 nm.

(2) Hole injection layer, hole transport layer The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon And the like. The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.

  The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and further preferably 1 nm to 100 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. .

(3) Electron injection layer, electron transport layer The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexes, organosilane derivatives, and the like.

  The thicknesses of the electron injection layer and the electron transport layer are each preferably 50 nm or less from the viewpoint of lowering the driving voltage. The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and further preferably 0.5 nm to 50 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(4) Hole blocking layer The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like. The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm. The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

(Protective layer)
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, a material having a planarizing action and a material having a function of preventing moisture and oxygen from entering the element are preferable. Specific examples, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O 3 , Y ₂ O _3, TiO ₂ and metal oxides, metal nitrides such as SiN _x, SiN _x O _y or the like of metallic _{oxynitride, MgF 2, LiF, AlF 3} , CaF 2 , etc. of the metal fluoride, polyethylene , Polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerizing a monomer composition containing a cyclic structure in the copolymer main chain Fluorine-containing copolymer having 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like. Of these, metal oxides, nitrides, and nitride oxides are preferable, and silicon oxides, nitrides, and nitride oxides are particularly preferable.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, vacuum ultraviolet CVD method, coating method, printing method, transfer method can be applied. In the present invention, a protective layer may be used as the conductive layer.

(Sealing)
Furthermore, the organic EL device of the present invention may be sealed using a sealing container. Further, a moisture absorbent or an inert liquid may be enclosed in a space between the sealing container and the light emitting element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

  As another sealing method, a so-called solid sealing method may be used. The solid sealing method is a method in which a protective layer is formed on an organic EL element, and then an adhesive layer and a barrier support layer are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated. The barrier support may be glass or the gas barrier laminate film of the present invention.

  As another sealing method, a so-called film sealing method may be used. The film sealing method is a method of providing an alternating laminate of an inorganic layer and an organic layer on an organic EL element. Before providing the alternate laminate, the organic EL element may be covered with a protective layer.

  The organic EL device of the present invention obtains light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. be able to. Regarding the driving method of the organic EL device of the present invention, each of JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in Japanese Patent Publication No. 2784615, US Pat. Nos. 5,828,429, and 6,023,308 can be applied.

  When the gas barrier laminate film of the present invention is used for organic EL or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. And the contents described in JP-A-2001-148291, JP-A-2001-221916, and JP-A-2001-231443 can be preferably employed. That is, the gas barrier laminate film of the present invention can be used not only as a base film for forming an organic EL device but also as a protective film or the like.

  The features of the present invention will be described more specifically with reference to examples and comparative 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 should not be construed as being limited by the specific examples shown below.

<Example 1>
(Preparation of laminated film of the present invention)
A polyethylene naphthalate film (manufactured by Teijin DuPont, trade name: Teonex Q65FA) was cut into a 20 cm square to produce a base film 1 for a laminated film.
1 g of the following compound (A) [manufactured by Nippon Kayaku Co., Ltd., KAYAMER series, PM-21] as an acrylate having a phosphate ester group, the following photopolymerizable compound [Kyoeisha Chemical Co., Ltd. 9 g of light acrylate BEPG-A] and 0.6 g of photopolymerization initiator [Ciba Geigy, IRGACURE907] were prepared and dissolved in 190 g of methyl ethyl ketone to obtain a coating solution. This coating solution was applied on the smooth surface of the base film using a wire bar with a wire bar (# 6), and an air-cooled metal halide lamp (160 W / cm) under a nitrogen purge with an oxygen concentration of 0.1% or less ( An organic layer having a film thickness of about 500 nm was formed by irradiating ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² . This was designated as film 2A. Moreover, the film which formed the organic layer into a film using the following compound (B) [the Kyoeisha Chemical Co., Ltd. make, light ester P-2M] instead of the compound (A) is 2B, the following compound (C) [Osaka The film in which the organic layer was formed using V # 3PA manufactured by Organic Chemical Co., Ltd. was designated as 2C.
Further, an inorganic layer made of silicon oxide (SiOx) was formed on the organic layers 2A to 2C. The inorganic layer was formed using a sputtering apparatus, using Si as a target, argon as a discharge gas, and oxygen as a reaction gas. The thickness of the inorganic layer was 50 nm, and the formed laminated films were 3A to 3C, respectively.
On the inorganic layers of the laminated films 3A to 3C, the coating solution used at the time of forming each organic layer is applied on the inorganic film made of silicon oxide with a wire bar (# 6), and the oxygen concentration is 0.1% or less. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge, an organic film having a film thickness of about 500 nm is irradiated by irradiating ultraviolet rays with an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ^2. Layers were formed to produce laminated films 4A to 4C composed of [organic layer / inorganic layer / organic layer / base material].
Moreover, about the laminated film 3C formed into a film, the organic layer and the inorganic layer were formed into a film on the surface opposite to the formed barrier layer by the above method, and [inorganic layer / organic layer / base material / organic layer / inorganic layer]. The laminated film 3C-2 comprised by this was produced.

<Comparative example>
The organic layer was formed by the same method as the film forming film 2A except that a polymerizable monomer having no phosphate ester group was used instead of the compound (A) used in the production of the organic layer film forming film 2A of Example 1. Layer film-forming films 2D, 2E, 2F, and 2G were produced. As a polymerizable monomer having no phosphate ester group, the following compound (D) [made by Shin-Nakamura Chemical Co., TOPOLEN], which is an acrylate having a hydroxyl group, is used for the film 2D, and the film 2E is an acrylate having a carboxylic acid. The following compound (E) [manufactured by Toa Gosei Co., Ltd., M5300] is used, the following compound (F) [Aldrich, AAEMA], which is an acrylate having an acetylacetone structure, is used for the film 2F, and the trifunctional acrylate is used for the film 2G. The following compound (G) [manufactured by Kyoeisha Chemical Co., Ltd., light acrylate TMP-A] was used. Moreover, the film 2H which formed the organic layer into a film using the liquid mixture of only said photopolymerizable compound and an initiator was also produced.
Further, a silicon oxide film of 50 nm was formed on the organic layers of the organic layer forming films 2D to 2H in the same manner as in Example 1 to produce laminated films 3D to 3H. On the inorganic layers of the laminated films 3D to 3H, the coating liquid used at the time of forming each organic layer is applied in the same manner as in Example 1, and a second organic layer having a film thickness of about 500 nm is formed by irradiating ultraviolet rays. Thus, laminated films 4D to 4H composed of [second organic layer / inorganic layer / organic layer / base material] were produced.

<Test example>
(Gas barrier property test during bending)
Laminated films 4A to 4H were cut into 10 cm × 10 cm, respectively, and both sides were bonded to form a columnar shape with the inorganic layer and the organic layer formed on the outside. The laminated film was rotated and conveyed at 30 cm / min with care so that the laminated film and the roller part were completely in contact with each other and the laminated film did not slip. Each laminated film was used after being conditioned for 8 hours in an environment of 25 ° C. and a relative humidity of 60%, and the above operation was performed in a laboratory under the same conditions. After the above operation, the oxygen transmission rate and water vapor transmission rate were set at 38 ° C. and relative humidity 10% or 90%, using the MOCON method (oxygen: MOCON OX-TRAN 2/20 L, water vapor: MOCON PERMATRAN-W (3) / 31). The results are shown in Table 1.

(Adhesion test)
In order to evaluate the adhesion of the laminated film, a cross-cut test based on JIS K5400 was performed. Cuts of 90 ° with respect to the film surface were made at 1 mm intervals on the surfaces of the laminated films 4A to 4H on the organic layer side, respectively, and 100 grids with 1 mm intervals were produced. A 2 cm wide Mylar tape [manufactured by Nitto Denko, polyester tape (No. 31B)] was applied thereto, and the tape attached using a tape peeling tester was peeled off. Of the 100 grids on the laminated film, the number (n) of the cells remaining without peeling was counted and evaluated. The results are shown in Table 2.

(Evaluation)
From Table 1, the gas barrier laminate films (laminated films 3A to 3C-2) obtained by laminating an inorganic layer and an organic layer containing a polymer having a phosphate ester group do not contain an inorganic layer and a polymer having a phosphate ester group. From the laminated film (laminated films 3D to 3H) laminated with the organic layer, it can be seen that the oxygen transmission rate and the water vapor transmission rate are excellent when the film is bent. Moreover, from Table 2, the laminated film (laminated film 4A-4C) provided with the organic layer containing the polymer which has a phosphate ester group has the organic layer and the inorganic layer closely_contact | adhered, and produces delamination. There was almost no. From these results, the gas barrier laminate film of the present invention is improved in adhesion between the organic layer and the inorganic layer by laminating the inorganic layer and the organic layer containing the polymer having a phosphate group. It can be seen that even when the stress applied to the inorganic layer is reduced, cracks and the like do not occur, and good gas barrier performance can be obtained.

<Example 2>
(Preparation of organic EL device using laminated film as substrate)
On the organic layer of the laminated film 4C, reactive evaporation was performed under vacuum while controlling the amount of Si evaporation and the amount of oxygen gas introduced to form a silicon oxide layer having a thickness of 60 nm as the second inorganic layer. The obtained laminated film was introduced into a vacuum chamber, and a transparent conductive layer (transparent electrode) made of an ITO thin film having a thickness of 200 nm was formed on the second inorganic layer by DC magnetron sputtering using an ITO target. This was designated as a film substrate 5C.
An aluminum lead wire was connected from the transparent electrode (ITO) of the film substrate 5C to form a laminated structure. The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylenedioxythiophene / polystyrenesulfonic acid [BAYER, Baytron P: solid content: 1.3% by mass], and then vacuum-dried at 150 ° C. for 2 hours, A hole-transporting organic thin film layer having a thickness of 100 nm was formed. This was designated as substrate X.

On the other hand, using a spin coater, a coating solution for a light-emitting organic thin film layer having the following composition is formed on one surface of a temporary support made of polyethersulfone [Sumitomo Bakelite Co., Ltd., Sumilite FS-1300] having a thickness of 188 μm. By coating and drying at room temperature, a light-emitting organic thin film layer having a thickness of 13 nm was formed on the temporary support. This was designated as transfer material Y.
Polyvinylcarbazole 40 parts by mass (Mw = 63000, manufactured by Aldrich)
Tris (2-phenylpyridine) iridium complex 1 part by mass (orthometalated complex)
1,200 parts by mass of 1,2-dichloroethane

  The light-emitting organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and a temporary support Was peeled off to form a light-emitting organic thin film layer on the upper surface of the substrate X. This was designated as substrate XY.

A patterned mask (a mask with a light emitting area of 5 mm × 5 mm) is placed on one side of a polyimide film [UPILEX-50S, manufactured by Ube Industries, Ltd.] having a thickness of 50 μm cut into 25 mm square, and a film thickness of 250 nm is formed by vapor deposition. Al was formed into a film, and LiF was formed into a film with a thickness of 3 nm by a vapor deposition method. A coating solution for an electron transporting organic thin film layer having the following composition is applied onto the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron having a thickness of 15 nm is obtained. A transportable organic thin film layer was formed on LiF. Furthermore, an aluminum lead wire was connected from the Al electrode, and this was used as a substrate Z.
Polyvinyl butyral 2000L 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol 3500 parts by mass An electron transporting compound having the following structure 20 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element was produced by bonding.

  When a direct voltage was applied to the obtained organic EL element using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.), the produced organic EL element emitted light well. The organic EL device was allowed to stand at 25 ° C. and 10% relative humidity at 90% and 90% for 12 hours for 10 days after the device was prepared, and the light was emitted in the same manner. However, the device was not deteriorated. As mentioned above, it turned out that the organic EL element of this invention shows high durability.

  The gas barrier laminate film of the present invention has high gas barrier performance and excellent bending resistance. For this reason, it can be effectively applied to a wide variety of articles that need to block water vapor, oxygen, and the like, and flexible articles. Moreover, according to the present invention, it is possible to provide a high-definition image display element having high durability, and it can be preferably applied to a flexible high-definition display. Therefore, the present invention has high industrial applicability.

Claims (18)

A method for producing a gas barrier laminate film having at least one inorganic layer and at least one organic layer on a substrate film, the acrylate monomer having a phosphate ester group, and the methacrylate monomer having a phosphate ester group Or forming the organic layer by polymerizing a monomer composition containing a mixture thereof, and the inorganic layer is formed of Si, Al, In, Sn, Zn, Ti, Cu, Ce, Zr, and Ta. A method for producing a gas barrier laminate film, comprising at least one of oxides, nitrides, and oxynitrides containing one or more metals selected from the group consisting of: The method for producing a gas barrier laminate film according to claim 1, wherein the acrylate monomer having a phosphate ester group and the methacrylate monomer having a phosphate ester group are represented by the following general formula (1).

[In General Formula (1), Z ¹ represents Ac ² —O—X ² —, a substituent having no polymerizable group or a hydrogen atom, Z ² represents Ac ³ —O—X ³ —, a polymerizable group. Each having no substituent or hydrogen atom, each of Ac ¹ , Ac ² and Ac ³ independently represents an acryloyl group or a methacryloyl group, and X ¹ , X ² and X ³ are each independently an alkylene group, an alkyleneoxy group, an alkylene An oxycarbonyl group, an alkylenecarbonyloxy group, or a combination thereof is represented. ] The method for producing a gas barrier laminate according to claim 2, wherein at least one of Z ¹ and Z ² is a hydrogen atom. The said monomer composition contains 1-50 mass% of monomers represented by the said General formula (1), The manufacturing method of the gas-barrier laminated film as described in any one of Claims 1-3 characterized by the above-mentioned. The said monomer composition contains a bifunctional acrylate monomer, a bifunctional methacrylate monomer, or these mixtures, The manufacturing method of the gas-barrier laminated film as described in any one of Claims 1-4 characterized by the above-mentioned. The said organic layer is formed into a film by flash vapor deposition, and the said monomer composition is superposed | polymerized in the vacuum of 100 Pa or less, The manufacture of the gas barrier laminated film as described in any one of Claims 1-5 characterized by the above-mentioned. Method. The method for producing a gas barrier laminate film according to any one of claims 1 to 6, wherein the organic layer and the inorganic layer are always laminated in a vacuum of 100 Pa or less. The manufacturing method of the gas-barrier laminated film as described in any one of Claims 1-7 with which the said monomer composition contains a photoinitiator. A gas barrier laminate film produced by the production method according to claim 1. A gas barrier laminate film having at least one inorganic layer and at least one organic layer on a base film, wherein the organic layer has an acrylate monomer having a phosphate ester group and a methacrylate having a phosphate ester group A polymer having a phosphate ester group obtained by polymerizing a monomer or a monomer containing a mixture thereof , and the inorganic layer includes Si, Al, In, Sn, Zn, Ti, Cu, Ce A gas barrier laminate film comprising at least one of oxides, nitrides, and oxynitrides containing at least one metal selected from Zr and Ta. The gas barrier laminate film according to claim 9 or 10, which has a structure in which the organic layer and the inorganic layer are laminated in this order on the base film. The gas barrier laminate film according to any one of claims 9 to 11, which has a structure in which the inorganic layer and the organic layer are laminated in this order on the base film. The gas barrier laminate film according to any one of claims 9 to 12, further comprising at least one inorganic layer and at least one organic layer on both surfaces of the base film. The gas barrier laminate film according to any one of claims 9 to 13, further comprising a transparent conductive layer. The oxygen transmission rate at 38 ° C. and 90% relative humidity is 0.02 ml / (m ² · day · atm) or less, and the water vapor transmission rate at 38 ° C. and 90% relative humidity is 0.01 g / (m ² · day). The gas barrier laminate film according to any one of claims 9 to 14, wherein: The image display element using the gas-barrier laminated | multilayer film as described in any one of Claims 9-15. The image display element according to claim 16, wherein the image display element is flexible. The image display element according to claim 16 or 17, wherein the image display element is an organic EL element.