JP5052418B2 - Barrier laminate, gas barrier film, device and optical member - Google Patents

Description

  The present invention relates to a barrier laminate, and a gas barrier film, device and optical member using the same.

In recent years, in the fields of liquid crystal display elements, organic EL elements (organic electroluminescent elements), and the like, a plastic film substrate that is light and does not break has started to be used instead of a glass substrate that is heavy and easily broken. However, from the viewpoint of blocking gas from the outside (sealing, gas barrier property), the plastic film substrate generally has a problem that it is inferior in water vapor barrier property as compared with a glass substrate. When a film substrate having a poor water vapor barrier property is used for a liquid crystal display element or an organic EL element, water vapor enters the liquid crystal cell and a display defect is likely to occur. In order to solve this problem, an inorganic layer having a barrier property is widely formed on a plastic film support. Specifically, silicon oxide is vapor-deposited on a plastic film support as disclosed in Patent Document 1, and aluminum oxide is vapor-deposited on a plastic film support as disclosed in Patent Document 2. It has been known. Further, Patent Document 3 discloses that a composite oxide of silicon oxide, aluminum oxide, indium and tin is formed on a plastic film support by a sputtering method. In this document, the best one is an inorganic layer. A gas barrier ability (water vapor transmission rate) of 0.011 g / m ² / day per layer is achieved. However, the gas barrier ability considered necessary for application to organic EL elements is 0.001 g / m ² / day or less, and the gas barrier ability of Patent Document 3 is not sufficient for the purpose of adapting to organic EL elements. Patent Document 4 describes that in a laminate of an inorganic oxide thin film layer and a modified polyvinyl alcohol resin layer, the modified polyvinyl alcohol resin layer contains a metal compound catalyst. That is, a low molecular complex is added to the modified polyvinyl alcohol resin layer. However, considering the recent demand for high barrier performance, the performance is not sufficient.

Japanese Examined Patent Publication No. 53-12953 (pages 1 to 3) JP 58-217344 A (pages 1 to 4) JP 2002-264274 A JP 2004-330673 A

  The object of the present invention is to solve the above-described problems, and to provide a barrier laminate having better barrier performance.

（一般式（１）中、Ｒ¹およびＲ³は、それぞれ、水素原子または置換基であり、Ｒ¹およびＲ³の少なくとも一方は、重合性基を含む。Ｒ²は、−（ＣＨＲ^c）−で表される基であり、Ｒ^cは水素原子または置換基である。）
一般式（２）

（一般式（２）中、Ｒ⁴は、一つ以上の置換基であり、いずれの環に含まれていてもよく、それぞれ水素原子または置換基であり、Ｒ⁴の少なくとも１つは、重合性基を含む。）
（７）有機層の表面に無機層が設けられている、（１）〜（６）のいずれか１項に記載のバリア性積層体。
（８）有機層と無機層を交互に積層し、少なくとも２層の無機層を有する、（１）〜（７）のいずれか１項に記載のバリア性積層体。
（９）無機層がＳｉまたはＡｌの、酸化物、窒化物または酸窒化物であることを特徴とする、（１）〜（８）のいずれか１項に記載のバリア性積層体。
（１０）無機層を反応性スパッタリング法によって成膜してなる、（１）〜（９）のいずれか１項に記載のバリア性積層体。
（１１）無機層がＣＶＤ法によって成膜してなる、（１）〜（９）のいずれか１項に記載のバリア性積層体。
（１２）支持体上に、（１）〜（１１）のいずれか１項に記載のバリア性積層体を設けたガスバリアフィルム。
（１３）（１２）に記載のガスバリアフィルムを基板に用いたデバイス。
（１４）（１２）に記載のガスバリアフィルムを用いて封止したデバイス。
（１５）（１）〜（１１）のいずれか１項に記載のバリア性積層体を用いて封止したデバイス。
（１６）前記デバイスが、電子デバイスである、（１３）〜（１５）のいずれか１項に記載のデバイス。
（１７）前記デバイスが、有機ＥＬ素子である、（１３）〜（１５）のいずれか１項に記載のデバイス。
（１８）（１）〜（１１）のいずれか１項に記載のバリア性積層体または（１２）に記載のガスバリアフィルムを用いた光学部材。 As a result of intensive studies by the inventor under the above problems, the above problems have been solved by the following means.
(1) A barrier laminate having at least one organic layer and at least one inorganic layer, wherein the organic layer contains a chelate ligand.
(2) The barrier laminate according to (1), wherein the organic layer contains a polymer compound as a main component, and a chelate ligand contained in the organic layer is chemically bonded to the polymer compound. body.
(3) The barrier laminate according to (1) or (2), wherein the organic layer is polymerized after or while applying the polymerizable compound.
(4) The chelating ligand according to any one of (1) to (3), wherein the chelating ligand is a chelating ligand capable of becoming a 5-membered or 6-membered ring structure after metal coordination. The barrier laminate according to the description.
(5) The barrier laminate according to any one of (1) to (4), wherein among the chelate ligands, an atom to which a metal coordinates is O or N.
(6) The chelate ligand is obtained by polymerizing at least one compound selected from a compound represented by the following general formula (1) and a compound represented by the general formula (2). The barrier laminate according to any one of (1) to (5).
General formula (1)

(In General Formula (1), R ¹ and R ³ are each a hydrogen atom or a substituent, and at least one of R ¹ and R ³ includes a polymerizable group. R ² is — (CHR ^c ). -R ^c is a hydrogen atom or a substituent.
General formula (2)

(In the general formula (2), R ⁴ is one or more substituents, which may be contained in any ring, each of which is a hydrogen atom or a substituent, and at least one of R ⁴ is polymerized. Contains a sex group.)
(7) The barrier laminate according to any one of (1) to (6), wherein an inorganic layer is provided on the surface of the organic layer.
(8) The barrier laminate according to any one of (1) to (7), wherein organic layers and inorganic layers are alternately laminated to have at least two inorganic layers.
(9) The barrier laminate according to any one of (1) to (8), wherein the inorganic layer is an oxide, nitride, or oxynitride of Si or Al.
(10) The barrier laminate according to any one of (1) to (9), wherein the inorganic layer is formed by a reactive sputtering method.
(11) The barrier laminate according to any one of (1) to (9), wherein the inorganic layer is formed by a CVD method.
(12) A gas barrier film in which the barrier laminate according to any one of (1) to (11) is provided on a support.
(13) A device using the gas barrier film according to (12) as a substrate.
(14) A device sealed using the gas barrier film according to (12).
(15) A device sealed using the barrier laminate according to any one of (1) to (11).
(16) The device according to any one of (13) to (15), wherein the device is an electronic device.
(17) The device according to any one of (13) to (15), wherein the device is an organic EL element.
(18) An optical member using the barrier laminate according to any one of (1) to (11) or the gas barrier film according to (12).

  According to the present invention, it is possible to obtain a gas barrier film having more excellent barrier properties.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. 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.

<Barrier laminate>
The barrier laminate of the present invention has at least one organic layer and at least one inorganic layer, and the organic layer contains a chelate ligand. Barrier property can be improved by setting it as the barriering laminated body which has such an organic layer.
In particular, when the organic layer contains a chelate ligand, metal migration in the initial stage of film formation of the adjacent inorganic layer is suppressed, and as a result of improved density of the inorganic layer, a barrier laminate having better barrier performance is obtained. can get. Therefore, the barrier laminate of the present invention preferably has a configuration in which an inorganic layer is provided on the surface of the organic layer. More preferably, it is a structure in which at least two organic layers having the above structure and at least one inorganic layer are alternately stacked. By setting it as such a structure, the adhesiveness of an organic layer and an inorganic layer improves, and barrier property improves more.

(Organic layer)
The organic layer in the present invention contains a chelate ligand, preferably an organic layer containing a polymer compound as a main component and the chelate ligand chemically bonded to the polymer compound. Here, the polymer compound as a main component means that the polymer compound is the first component constituting the organic layer, and usually 80% by weight or more of the organic layer is the polymer compound. The chelate ligand is more preferably a chelate ligand that can form a 5-membered or 6-membered ring structure after metal coordination, and more preferably, the atom to which the metal coordinates is O or N Chelating ligand. The organic layer of the present invention is preferably formed by polymerizing any one or more of the compounds represented by the following general formulas (1) to (5), more preferably the general formula (1). It is formed by polymerizing any one or more of the compounds represented by (5) and another polymerizable compound. In particular, in the present invention, any one or more of the compounds represented by the general formula (1) or (2) is polymerized with another polymerizable compound.

（一般式（１）中、Ｒ¹およびＲ³は、それぞれ、メチル基またはその他の置換基であり、Ｒ¹およびＲ³の少なくとも一方は、重合性基を含む。Ｒ²は、−（ＣＨＲ^c）−で表される基であり、Ｒ^cは水素原子または置換基である。） General formula (1)

(In General Formula (1), R ¹ and R ³ are each a methyl group or another substituent, and at least one of R ¹ and R ³ includes a polymerizable group. R ² is — (CHR ^c ) a group represented by-, and R ^c is a hydrogen atom or a substituent.)

Any substituent may be used for R ¹ and R ^3, and examples thereof include an alkyl group, an aryl group, and an alkoxy group. Examples of the substituent containing a polymerizable group include a substituent containing a radical polymerizable group. As the polymerizable group, an acrylic group, a methacryl group, and a vinyl group are preferable, and an acrylic group is particularly preferable. R ² is, - (CHR ^c) - in a group represented as the substituent in R ^c, but also include the same as the substituents exemplified in R ¹ and R ^3, R ^c is a hydrogen atom preferable.

（一般式（２）中、Ｒ⁴は、それぞれ、水素原子または置換基であり、Ｒ⁴の少なくとも１つは、重合性基を含む。） General formula (2)

(In general formula (2), each R ⁴ is a hydrogen atom or a substituent, and at least one of R ⁴ includes a polymerizable group.)

Examples of the substituent for R ⁴ include the same substituents as those for R ¹ and R ³ . Of R ⁴ , those containing a polymerizable group are preferably acrylic groups. R ⁴ preferably has a polymerizable group on the side to which the OH group is bonded.

（一般式（３）中、Ｒ⁵およびＲ⁸は、それぞれ、水素原子または置換基であり、Ｒ⁵およびＲ⁸の少なくとも一方は、重合性基を含む。Ｒ⁶は、−（ＣＲ^aＲ^b）−で表される基であり、Ｒ^aおよびＲ^bはそれぞれ水素原子または置換基である。Ｒ⁷は、水素原子または置換基である） General formula (3)

(In General Formula (3), R ⁵ and R ⁸ are each a hydrogen atom or a substituent, and at least one of R ⁵ and R ⁸ includes a polymerizable group. R ⁶ is — (CR ^a R ^b )-, wherein R ^a and R ^b are each a hydrogen atom or a substituent, and R ⁷ is a hydrogen atom or a substituent)

Examples of the substituent for R ⁵ and R ⁸ include the same substituents as those described for R ¹ and R ³ . When R ⁵ and R ⁸ each contain a polymerizable group, it is preferable that at least two methylene chains are directly connected to the N atom, and those containing a polymerizable group among R ⁵ and R ⁸ Each is preferably an acrylic group.
^Examples of the substituent for R ^a and R ^b include the same substituents as those described for R ¹ and R ³ . R ⁶ is preferably methylene.
Examples of the substituent for R ⁷ include the same substituents as those described for R ¹ and R ³ . R ⁷ is preferably a hydrogen atom.

（一般式（４）中、Ｒ⁹は、それぞれ、水素原子または置換基であり、Ｒ⁹の少なくとも１つは、重合性基を含む。Ｒ¹⁰は、水素原子または置換基である。） General formula (4)

(In General Formula (4), each R ⁹ is a hydrogen atom or a substituent, and at least one of R ⁹ includes a polymerizable group. R ¹⁰ is a hydrogen atom or a substituent.)

Examples of the substituent for R ⁹ include the same substituents as those for R ¹ and R ³ . Among R ⁹ , those containing a polymerizable group are preferably acrylic groups. Examples of the substituent for R ¹⁰ include the same substituents as those described for R ¹ and R ³ . R ¹⁰ is preferably a hydrogen atom.

（一般式（５）中、Ｒ¹¹は、それぞれ、水素原子または置換基であり、Ｒ¹¹の少なくとも１つは、重合性基を含む。Ｒ¹²、Ｒ¹³およびＲ¹⁴は、それぞれ、水素原子または置換基である。） General formula (5)

(In the general formula (5), R ¹¹ is a hydrogen atom or a substituent, and at least one of R ¹¹ includes a polymerizable group. R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom. Or a substituent.)

Examples of the substituent for R ¹² and R ¹³ include the same substituents as those described for R ¹ and R ³ . R ¹² and R ¹³ are each preferably a hydrogen atom.
Examples of the substituent for R ¹⁴ include the same substituents as those described for R ¹ and R ³ . R ¹⁴ is preferably a hydrogen atom.
Examples of the substituent for R ¹¹ include the same substituents as those for R ¹ and R ³ . Among R ¹¹ , those containing a polymerizable group are preferably acrylic groups.

  Although the polymerizable compound which has a chelate ligand used preferably by this invention is illustrated below, it cannot be overemphasized that this invention is not limited to these.

As other polymerizable compounds in the organic layer of the present invention, known polymerizable compounds can be widely adopted, and examples thereof include vinyl compounds, (meth) acrylate compounds, epoxy compounds, oxetane compounds, vinyl compounds, ( A meth) acrylate compound is preferred, and an acrylate compound is more preferred.
In the present invention, the ratio (weight ratio) of the compounds represented by the general formulas (1) to (5) and other polymerizable compounds is preferably 1:19 to 1: 1, and 1: 9 More preferably, it is ˜1: 4.

(Polymerization initiator)
The organic layer in the present invention is usually obtained by coating and curing a polymerizable composition containing a polymerizable compound, but the polymerizable composition may contain a polymerization initiator. When using a photoinitiator, it is preferable that the content is 0.1 mol% or more of the total amount of the polymerizable compounds, and more preferably 0.5 to 2 mol%. By setting it as such a composition, the polymerization reaction via an active component production | generation reaction can be controlled appropriately. Examples of the photopolymerization initiator include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Sartomer). Etc.) and oligomer type Ezacure KIP series.

(Formation method of organic layer)
The method for forming the organic layer is not particularly defined, but it is preferably formed by polymerizing the polymerizable compound after coating or while coating.
More specifically, it can be formed by a solution coating method or a vacuum film forming method. Examples of the solution 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, a slide coating method, or a method described in US Pat. No. 2,681,294. It can apply | coat by the extrusion coat method which uses a hopper. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vacuum evaporation and plasma CVD, are preferable. In the present invention, a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as disclosed in Japanese Patent Application Laid-Open Nos. 2000-323273 and 2004-25732 may be used.

In the present invention, a composition containing a polymerizable compound is usually cured by irradiation with light, but the irradiation light 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 employed 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 in the present invention is preferably smooth and has 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 groups among all the polymerizable groups in the monomer mixture. The polymerization rate can be quantified by an infrared absorption method.

The film thickness of the organic layer is not particularly limited, but if it is too thin, it is difficult to obtain film thickness uniformity, and if it is too thick, cracks are generated due to external force and the barrier property is lowered. From this viewpoint, the thickness of the organic layer is preferably 50 nm to 2000 nm, and more preferably 200 nm to 1500 nm.
The organic layer is preferably smooth as described above. The smoothness of the organic layer is preferably less than 1 nm and more preferably less than 0.5 nm as an average roughness (Ra value) of 1 μm square. 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.
It is preferable to laminate two or more organic layers. In this case, at least one layer may be the organic layer described above, and the other organic layer may be the organic layer described above or another organic layer. In addition, as one layer of the organic layer, as disclosed in US 2004-46497, the interface with the inorganic layer is not clear and the composition changes continuously in the film thickness direction. Also good.

(Inorganic layer)
The inorganic layer 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 a physical vapor deposition method (PVD) such as a vapor deposition method, a sputtering method, and an ion plating method, various chemical vapor deposition methods (CVD), and a liquid phase growth method such as plating and a sol-gel method. 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, oxycarbide, or the like containing at least one metal selected from Sn, Zn, Ti, Cu, Ce, or Ta can be preferably used. Among these, a metal oxide, nitride, or oxynitride selected from Si, Al, In, Sn, Zn, and Ti is preferable, and a metal oxide, nitride, or oxynitride of Si or Al is particularly preferable. These may contain other elements as secondary components.
The smoothness of the inorganic layer formed according to the present invention is preferably less than 1 nm, more preferably 0.5 nm or less, as an average roughness (Ra value) of 1 μm square. 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.

  Although it does not specifically limit regarding the thickness of an inorganic layer, It attaches to 1 layer, Usually, it exists in the range of 5-500 nm, Preferably it is 10-200 nm. 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.

(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. When the inorganic layer is formed by a vacuum film forming method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method, the organic layer is also preferably formed by a vacuum film forming method such as the flash vapor deposition method. . During film formation of the barrier layer, it is particularly preferable to always laminate the organic layer and the inorganic layer in a vacuum of 1000 Pa or less without returning to atmospheric pressure in the middle. The pressure is more preferably 100 Pa or less, more preferably 50 Pa or less, and further preferably 20 Pa or less.
In particular, the present invention can exhibit high barrier properties when at least two organic layers and at least two inorganic layers are alternately laminated. Furthermore, in this invention, the adhesiveness of this organic layer and this inorganic layer improves by providing an inorganic layer on the surface of the organic layer mentioned above, and is more preferable.

(Functional layer)
In the laminate of the present invention, a functional layer may be provided on the barrier laminate or at other positions. 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, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, and antifouling layers. , Printing layer, easy adhesion layer and the like.

Applications of Barrier Laminate The barrier laminate of the present invention is usually provided on a support, and can be used for various applications by selecting this support. In addition to the base film, the support includes various devices, optical members, and the like. Specifically, the barrier laminate of the present invention can be used as a barrier layer of a gas barrier film. The barrier laminate and gas barrier film of the present invention can be used for sealing devices that require barrier properties. The barrier laminate and gas barrier film of the present invention can also be applied to optical members. Hereinafter, these will be described in detail.

<Gas barrier film>
The gas barrier film has a base film and a barrier laminate formed on the base film. In the gas barrier film, the barrier laminate of the present invention 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 of the laminate of the present invention may be an inorganic layer or an organic layer.
The gas barrier film in the present invention is a film substrate having a barrier layer having a function of blocking oxygen, moisture, nitrogen oxides, sulfur oxides, ozone and the like in the atmosphere.
Although there is no restriction | limiting in particular regarding the number of layers which comprise a gas barrier film, Typically, 2-30 layers are preferable, and 3-20 layers are more preferable.
A gas barrier film may have structural components (for example, functional layers, such as an easily bonding layer) other than a barriering laminated body and a base film. 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).

(Plastic film)
The gas barrier film in the present invention usually uses a plastic film as the base film. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a laminate such as an organic layer and an inorganic layer, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When the gas barrier film of the present invention is used as a substrate for a device such as an organic EL element described later, the plastic film is preferably made of a material having heat resistance. Specifically, it is preferable that the glass transition temperature (Tg) is 100 ° C. or higher and / or the linear thermal expansion coefficient is 40 ppm / ° C. or lower and is made of a transparent material having high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive. As such a thermoplastic resin, for example, polyethylene naphthalate (PEN: 120 ° C.), 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: Japanese Patent Laid-Open No. 2001-150584 compound: 162 ° C.), polyimide (for example, Mitsubishi Gas Chemical) Neoprim: 260 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of JP 2000-227603 A) : 205 ° C), acryloyl compound (Compound described in JP-A 2002-80616: 300 ° C. or more) (the parenthesized data are Tg). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  When the gas barrier film of the present invention is used in combination with a polarizing plate, it is preferable that the barrier laminate of the gas barrier film faces the inside of the cell and is arranged on the innermost side (adjacent to the element). At this time, since the gas barrier film is disposed inside the cell from the polarizing plate, the retardation value of the gas barrier film is important. The usage form of the gas barrier film in such an embodiment includes a gas barrier film using a base film having a retardation value of 10 nm or less and a circularly polarizing plate (1/4 wavelength plate + (1/2 wavelength plate) + linearly polarizing plate. ) Or a linear barrier plate combined with a gas barrier film using a base film having a retardation value of 100 nm to 180 nm, which can be used as a quarter wavelength plate.

As a base film having a retardation of 10 nm or less, cellulose triacetate (Fuji Film Co., Ltd .: Fuji Tac), polycarbonate (Teijin Chemicals Co., Ltd .: Pure Ace, Kaneka: Elmec Co., Ltd.), cycloolefin polymer (JSR Co., Ltd.) ): Arton, Nippon Zeon Co., Ltd .: Zeonoa), cycloolefin copolymer (Mitsui Chemicals Co., Ltd .: Appel (pellet), Polyplastic Co., Ltd .: Topas (pellet)) Polyarylate (Unitika Co., Ltd.): U100 (pellet) )), Transparent polyimide (Mitsubishi Gas Chemical Co., Ltd .: Neoprim) and the like.
Moreover, as a quarter wavelength plate, the film adjusted to the desired retardation value by extending | stretching said film suitably can be used.

Since the gas barrier film of the present invention is used as a device such as an organic EL element, the plastic film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. It is. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. be able to.
Even when the gas barrier film of the present invention is used for display, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.
The thickness of the plastic film used for the gas barrier film of the present invention is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer 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.

<Device>
The barrier laminate and gas barrier film of the present invention can be preferably used for devices whose performance is deteriorated by chemical components in the air (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.). Examples of the device include electronic devices such as an organic EL element, a liquid crystal display element, a thin film transistor, a touch panel, electronic paper, and a solar cell, and are preferably used for the organic EL element.

  The barrier laminate of the present invention can also be used for device film sealing. That is, it is a method of providing the barrier laminate of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the barrier laminate.

 The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after forming a protective layer on the device, an adhesive layer and a gas barrier film 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.

(Organic EL device)
Examples of organic EL elements using a gas barrier film are described in detail in Japanese Patent Application Laid-Open No. 2007-30387.

(Liquid crystal display element)
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 film in the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, 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, in order from the bottom, 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 It has a structure consisting of a film. Of these, the substrate of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, 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 type of the liquid crystal cell is not particularly limited, but more preferably TN type (Twisted Nematic), STN type (Super Twisted Nematic), HAN type (Hybrid Aligned Nematic), VA type (Vertically Alignment), ECB type (Electrically Controlled Birefringence) OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the adhesive layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited. For example, it is composed of a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, a tandem structure type, or the like. Amorphous silicon solar cell elements, III-V compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), copper I-III-VI such as / indium / selenium (so-called CIS), copper / indium / gallium / selenium (so-called CIGS), copper / indium / gallium / selenium / sulfur (so-called CIGSS), etc. Group compound semiconductor solar cell elements, dye-sensitized solar cell elements, organic solar cell elements, and the like. Among these, in the present invention, the solar cell element is made of a copper / indium / selenium system (so-called CIS system), a copper / indium / gallium / selenium system (so-called CIGS system), copper / indium / gallium / selenium / sulfur. It is preferable that it is an I-III-VI group compound semiconductor solar cell element, such as a system (so-called CIGSS system).

(Other)
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. And solar cells described in the electronic paper.

<Optical member>
Examples of the optical member using the gas barrier film of the present invention include a circularly polarizing plate.
(Circularly polarizing plate)
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate using the gas barrier film of the present invention as a substrate. In this case, the lamination is performed so that the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, one that is stretched in a direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

  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.

<Synthesis of monomer>
(Synthesis of 1-aminonaphthalene)
According to the following scheme 1, 1-aminonaphthalene was synthesized. To a mixed solvent of 150 ml of isopropyl alcohol and 25 ml of water, 50 g of iron powder and 1 g of ammonium chloride were added and heated to 90 ° C. A solution prepared by dissolving 25 g of 1-nitronaphthalene (manufactured by Aldrich) in 100 ml of isopropyl alcohol was slowly added dropwise and stirred. After the reaction, it was filtered, concentrated with an evaporator, precipitated, and filtered again to obtain 18.31 g of 1-aminonaphthalene. Identification was performed by mass spectrometry, H-NMR and IR.

Scheme 1

(Synthesis of N-naphthylacrylamide)
According to the following scheme 2, N-naphthylacrylamide was synthesized. 15 g of 1-aminonaphthalene was dissolved in 100 ml of dichloromethane, and 100 ml of water and 13 g of sodium hydrogen carbonate were added and stirred. Next, 9.5 g of acrylic acid chloride was added and stirred sufficiently to extract the N-naphthylacrylamide fraction. This was purified by column chromatography to obtain 17 g of N-naphthylacrylamide. Identification was performed by mass spectrometry, H-NMR and IR.

Scheme 2

(Synthesis of N, 5- (8-hydroxyquinolinyl) acrylamide)
According to the following scheme 3, N, 8-hydroxyquinolinylacrylamide was synthesized. 25 g of 5-amino-8-hydroxyquinoline dihydrochloride (manufactured by Aldrich) was dissolved in 100 ml of dichloromethane, and 100 ml of water and 40 g of sodium bicarbonate were added and stirred. Next, 9.7 g of acrylic acid chloride was added and sufficiently stirred, and the N-naphthylacrylamide fraction was extracted. This was purified by column chromatography to obtain 18.75 g of N, 8-hydroxyquinolinylacrylamide. Identification was performed by mass spectrometry, H-NMR and IR.

Scheme 3

<Production of gas barrier film BF-1>
(Production of organic layer)
On a polyethylene naphthalate film (Teijin DuPont, Teonex Q65FA, thickness 100 μm), the following compound 1 and compound 2 were mixed at a 1: 1 (weight ratio) (total 20 g), and an ultraviolet polymerization initiator ( Ciba Specialty Chemicals, trade name: Ciba Irgacure 907) 0.6 g and 2-butanone 190 g were added to prepare a polymerizable composition. The polymerizable composition was applied using a wire bar so that the liquid thickness was 5 μm. After drying at room temperature, the organic layer is cured by irradiating UV light from a high-pressure mercury lamp (accumulated dose of about ² J / cm ² ) in a chamber in which the oxygen concentration is 0.1% by the nitrogen substitution method. An organic layer having a thickness of 1000 nm ± 50 nm was formed (O-1).

Compound 1

Compound 2

(Preparation of inorganic layer)
The organic layer (O-1) was carried into a sputtering apparatus, and plasma discharge was performed using Al as a target and Ar as a discharge gas. While monitoring the plasma emission so as to achieve the stoichiometric ratio of Al ₂ O ₃ , the flow rate of O ₂ as a reaction gas was controlled, and Al ₂ O ₃ was formed to a thickness of 100 nm to obtain a barrier laminate. (BF-1).

<Preparation of gas barrier film BF-2>
In preparation of gas barrier film BF-1, the compound 2 was replaced with the following compound 3, and others were performed similarly, and the organic layer was formed (O-2). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-1, and the gas barrier film (BF-2) was obtained.

Compound 3

<Preparation of gas barrier film BF-3>
In preparation of gas barrier film BF-1, the compound 2 was replaced with the following compound 4, and others were performed similarly, and the organic layer was formed (O-3). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-1, and the gas barrier film (BF-3) was obtained.

Compound 4

<Preparation of gas barrier film BF-4>
In preparation of gas barrier film BF-1, the compound 2 was replaced with the following compound 5, and others were performed similarly, and the organic layer was formed (O-4). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-1, and the gas barrier film (BF-4) was obtained.

Compound 5

 About the obtained gas barrier film, the water-vapor-permeation rate was measured with the following method.

<Measurement of water vapor transmission rate by calcium method>
The water vapor transmission rate (g / m ² / day) was measured using the method described in G. NISATO, PCPBOUTEN, PJSLIKKERVEER et al. SID Conference Record of the International Display Research Conference, pages 1435-1438. The temperature at this time was 40 ° C. and the relative humidity was 90%. The results are shown in the table below.

<Production of gas barrier film BF-5>
It carried out similarly to preparation of gas barrier film BF-1, and formed the organic layer (O-1). Furthermore, the organic layer (O-1) was carried into a sputtering apparatus, and plasma discharge was performed using Si as a target and Ar as a discharge gas. While monitoring the plasma emission so as to achieve the stoichiometric ratio of Si ₃ N ₄ , the flow rate of N ₂ was controlled as a reaction gas, and Si ₃ N ₄ was formed to a thickness of 100 nm to obtain a gas barrier film (BF− 5).

<Production of gas barrier film BF-6>
It carried out similarly to preparation of gas barrier film BF-2, and formed the organic layer (O-2). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-5, and the gas barrier film (BF-6) was obtained.

<Production of gas barrier film BF-7>
It carried out similarly to preparation of gas barrier film BF-3, and formed the organic layer (O-3). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-5, and the gas barrier film (BF-7) was obtained.

<Production of gas barrier film BF-8>
It carried out similarly to preparation of gas barrier film BF-4, and formed the organic layer (O-4). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-5, and the gas barrier film (BF-8) was obtained.

 About the obtained gas barrier film, the water-vapor-permeation rate was measured by the method similar to the above.

<Production of gas barrier film BF-9>
It carried out similarly to preparation of gas barrier film BF-1, and formed the organic layer (O-1). Furthermore, the organic layer (O-1) was carried into a CVD apparatus, and silane gas (SiH ₄ ), ammonia gas (NH ₃ ), and nitrogen gas (N ₂ ) were introduced. An RF discharge power having a frequency of 13.56 MHz is applied to form a Si ₃ N ₄ layer (inorganic layer) having a film thickness of 100 nm at a temperature of 25 ° C. and a film forming pressure of 10 Pa, thereby producing a gas barrier film (BF-9). did.

<Production of gas barrier film BF-10>
It carried out similarly to preparation of gas barrier film BF-2, and formed the organic layer (O-2). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-9, and the gas barrier film (BF-10) was obtained.

<Preparation of gas barrier film BF-11>
It carried out similarly to preparation of gas barrier film BF-3, and formed the organic layer (O-3). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-9, and the gas barrier film (BF-11) was obtained.

<Production of gas barrier film BF-12>
It carried out similarly to preparation of gas barrier film BF-4, and formed the organic layer (O-4). Furthermore, the inorganic layer was formed similarly to preparation of gas barrier film BF-9, and the gas barrier film (BF-12) was obtained.

 About the obtained gas barrier film, the water-vapor-permeation rate was measured by the method similar to the above.

  As is clear from the above results, it is clear that the barrier performance is improved when a chelate ligand is added to the organic layer. Furthermore, the same effect can be confirmed even when the inorganic layer is formed by the CVD method.

Evaluation with Organic EL Light Emitting Element In order to evaluate the barrier property, an organic EL element that produces a black spot (dark spot) defect with water vapor or oxygen was prepared and evaluated. First, a conductive glass substrate having an ITO film (surface resistance value 10Ω / □) was washed with 2-propanol, and then subjected to UV-ozone treatment for 10 minutes. The following compound layers were sequentially deposited on this substrate (anode) by vacuum deposition.
(First hole transport layer)
Copper phthalocyanine: film thickness 10nm
(Second hole transport layer)
N, N′-diphenyl-N, N′-dinaphthylbenzidine: film thickness 40 nm
(Light emitting layer and electron transport layer)
Tris (8-hydroxyquinolinato) aluminum: film thickness 60nm
(Electron injection layer)
Lithium fluoride: film thickness 1nm
On top of this, metal aluminum was deposited to a thickness of 100 nm to form a cathode, and a 3 μm thick silicon nitride film was formed thereon by a parallel plate CVD method to produce an organic EL device.
Next, using the thermosetting adhesive (Epotech 310, Daizonitomoly Co., Ltd.), on the prepared organic EL element and each of the gas barrier films prepared above, the barrier layer is on the organic EL element side. And heated at 65 ° C. for 3 hours to cure the adhesive. 20 organic EL elements sealed in this way were prepared.
The organic EL element immediately after production was made to emit light by applying a voltage of 7 V using a source measure unit (SMU2400 type, manufactured by Keithley). When the surface of the light emitting surface was observed using a microscope, it was confirmed that all the elements gave uniform light emission without dark spots.
Finally, each element was allowed to stand in a dark room at 60 ° C. and 90% relative humidity for 24 hours, and then the light emitting surface was observed. The ratio of elements in which dark spots larger than 300 μm in diameter were observed was defined as the failure rate, and the failure rate of each element was calculated. The failure rate was as good as 5% or less for all the elements of the present invention.

  Since the gas barrier film of the present invention has high barrier performance, it can be widely used in various devices that require barrier properties. In the gas barrier film of the present invention, since the smoothness of the organic layer can be improved, the inorganic layer can also be provided smoothly. As a result, the smoothness of the outermost surface can be improved, and the performance of the device formed on the gas barrier film can be improved.

Claims (16)

Has at least one organic layer and at least one inorganic layer, the organic layer is a free Muba rear laminate chelating ligand,
The chelate ligand is obtained by polymerizing at least one compound selected from the compound represented by the following general formula (1) and the compound represented by the general formula (2) with another polymerizable compound. , Barrier laminate.
General formula (1)

(In General Formula (1), R ¹ and R ³ are each a hydrogen atom or a substituent, and at least one of R ¹ and R ³ includes a polymerizable group. R ² is — (CHR ^c ). -R ^c is a hydrogen atom or a substituent.
General formula (2)

(In the general formula (2), R ⁴ is one or more substituents, which may be contained in any ring, each of which is a hydrogen atom or a substituent, and at least one of R ⁴ is polymerized. Contains a sex group.)   The barrier laminate according to claim 1, wherein the organic layer contains a polymer compound as a main component, and a chelate ligand contained in the organic layer is chemically bonded to the polymer compound.   The barrier laminate according to claim 1 or 2, wherein the organic layer is polymerized after or while applying the polymerizable compound.   The barrier laminate according to any one of claims 1 to 3, wherein the chelate ligand is a chelate ligand capable of becoming a 5-membered or 6-membered ring structure after metal coordination. body. The barrier laminate according to any one of claims 1 to 4 , wherein an inorganic layer is provided on the surface of the organic layer. The barrier laminate according to any one of claims 1 to 5 , wherein organic layers and inorganic layers are alternately laminated to have at least two inorganic layers. Inorganic layer is Si or Al, an oxide, characterized in that it is a nitride or oxynitride, barrier laminate according to any one of claims 1-6. The barrier laminate according to any one of claims 1 to 7 , wherein the inorganic layer is formed by a reactive sputtering method. The barrier laminate according to any one of claims 1 to 7 , wherein the inorganic layer is formed by a CVD method. On the support, the gas barrier film having a barrier laminate according to any one of claims 1-9. A device using the gas barrier film according to claim 10 as a substrate. A device sealed using the gas barrier film according to claim 10 . A device sealed up with a barrier laminate according to any one of claims 1-9. The device according to any one of claims 11 to 13 , wherein the device is an electronic device. The device according to any one of claims 11 to 13 , wherein the device is an organic EL element. The optical member using the gas barrier film according to the barrier laminate or claim 10 according to any one of claims 1-9.