JP5580561B2 - Barrier laminate, gas barrier film, and method for producing barrier laminate - Google Patents

Description

  The present invention relates to a novel barrier laminate, a gas barrier film, and a method for producing a barrier laminate. In particular, the present invention relates to a gas barrier film and the like preferably used as a solar cell member.

 A film having a property of blocking permeation of water vapor and oxygen, that is, a so-called gas barrier property (gas barrier film) has been conventionally studied. In order to improve the gas barrier property of a gas barrier film, forming an inorganic layer by methods, such as sputtering and plasma CVD method, is performed (patent document 1).

 Gas barrier films are used in various applications, and in recent years, application to electronic paper or the like has been studied as a sheet for sealing solar cells (Patent Document 2). When used for a solar cell or the like, a relatively large area is required, so that it is required to increase the production efficiency (film forming speed and cost) of the barrier film. However, until now, various studies have been made on enhancing the barrier properties of gas barrier films, but sufficient studies have not been conducted on enhancing production efficiency.

JP-A-8-165368 JP 2009-49252 A

From the viewpoint of enhancing the barrier property of the barrier film, the object is achieved by forming the inorganic layer by sputtering or plasma CVD. However, sputtering has a very slow film formation speed, and the plasma CVD method has a problem that the cost is high and it is not a practical method for use where a large-area gas barrier film is required.
The present invention aims to supply a barrier film having a large area with high productivity, and forms an inorganic layer without using a method such as sputtering or CVD, and has a high barrier property. An object of the present invention is to provide a conductive laminate and a barrier film using the barrier laminate.

Under such circumstances, we investigated the formation of an inorganic layer by plasma-assisted vapor deposition for the purpose of forming an inorganic layer by a method having a higher deposition rate than sputtering or CVD. When it was adopted, it was found that the organic layer, which is the underlying layer of the inorganic layer, was damaged by the plasma. As a result of further studies by the inventors of the present application, it has been found that this disadvantage can be eliminated by employing a resin having a carbon cyclic skeleton as the material of the organic layer, and the present invention has been completed. Specifically, the problems of the present invention have been solved by the following means.
(1) It has at least one organic layer and at least one inorganic layer, the organic layer contains a resin having a carbon cyclic skeleton, and the inorganic layer is formed by a plasma assisted deposition method. A barrier laminate.
(2) The barrier laminate according to (1), wherein the resin contained in the organic layer is an ultraviolet curable resin.
(3) The barrier laminate according to (1) or (2), wherein the resin contained in the organic layer is a resin obtained by curing (meth) acrylate having a carbon cyclic skeleton.
(4) The barrier laminate according to any one of (1) to (3), wherein the inorganic layer contains silicon and / or aluminum.
(5) The barrier laminate according to any one of (1) to (4), wherein the plasma used at the time of forming the inorganic layer is argon gas, oxygen gas, or a mixed gas thereof.
(6) The barrier according to any one of (1) to (5), wherein the barrier laminate is formed by alternately laminating at least two organic layers and at least two inorganic layers. Laminate.
(7) The barrier laminate according to any one of (1) to (6), wherein the resin contained in the organic layer is a resin obtained by curing (meth) acrylate having an aromatic ring.
(8) The barrier laminate according to any one of (1) to (7), wherein the resin contained in the organic layer is a resin obtained by curing polyfunctional (meth) acrylate.
(9) A gas barrier film in which the barrier laminate according to any one of (1) to (8) is provided on a base film.
(10) A composite film having a structure in which two gas barrier films according to (9) are bonded with the barrier laminate side facing inward.
(11) A solar cell member using the gas barrier film according to (9) or the composite film according to (10).
(12) A method for producing a barrier laminate comprising at least one organic layer and at least one inorganic layer, wherein the organic layer includes a resin having a carbon cyclic skeleton, wherein the inorganic layer is plasma The manufacturing method of a barriering laminated body including forming by an assist vapor deposition method.
(13) The method for producing a barrier laminate according to (12), comprising forming the organic layer by curing a polymerizable composition containing (meth) acrylate having an aromatic ring.

  According to the present invention, a barrier laminate and a gas barrier film having excellent barrier properties can be produced at a high film-forming speed, and therefore, it can be preferably used when used in large quantities such as solar cell sheets.

It is a figure which shows an example of the preferable aspect of the gas barrier film of this invention. It is a figure which shows another example of the preferable aspect of the gas barrier film of this invention. It is a figure which shows an example of the preferable aspect of the composite film of this invention.

  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 includes at least one organic layer and at least one inorganic layer, and preferably has a structure in which an inorganic layer is provided on the surface of the organic layer, more preferably And a structure in which at least two organic layers and at least two inorganic layers are alternately laminated.
Although there is no restriction | limiting in particular regarding the number of layers which comprise a barriering laminated body, Typically 2-30 layers are preferable, and 3-20 layers are more preferable. Moreover, you may include other structural layers other than an organic layer and an inorganic layer.

(Organic layer)
The organic layer in the present invention includes a resin having a carbon cyclic skeleton. The carbocyclic skeleton includes benzene ring skeleton, biphenyl skeleton, naphthalene skeleton, binaphthyl skeleton, azulene skeleton, biphenylene skeleton, acenaphthylene skeleton, phenanthrene skeleton, anthracene skeleton, triphenylene skeleton, pyrene skeleton, chrysene skeleton, naphthacene skeleton, picene skeleton, and perylene. Preferred examples include a skeleton and a benzopyrene skeleton. In the present invention, the carbocyclic skeleton preferably has one or more aromatic rings, and more preferably a resin obtained by curing a polymerizable compound having two or more aromatic rings. By adopting a resin having a carbocyclic skeleton having one or more aromatic rings, a layer that is more difficult to be decomposed even during a plasma process can be formed. As a result, the barrier property tends to be improved.

  The resin contained in the organic layer in the present invention is preferably a resin having a three-dimensional crosslinkability. By adopting such a resin, the organic layer can have a denser structure.

  The resin contained in the organic layer in the present invention is preferably an ultraviolet curable resin, and more preferably a resin obtained by curing (meth) acrylate having a carbon cyclic skeleton. In particular, in the present invention, a resin obtained by curing (meth) acrylate having an aromatic ring is more preferable. By adopting such a resin, a cured film can be formed quickly, and the (meth) acrylate may be monofunctional or polyfunctional, but is preferably polyfunctional. By adopting polyfunctional (meth) acrylate, three-dimensional crosslinkability can be provided.

In the following, (meth) acrylates preferably used in the present invention are exemplified, but it goes without saying that the present invention is not limited to these.

The organic layer of the present invention is preferably obtained by curing a polymerizable composition containing a polymerizable compound as described above and a polymerization initiator, and the polymerizable monomer component contained in the polymerizable composition is 50 It is preferable that ˜100% by weight is a (meth) acrylate having a carbocyclic skeleton.
Further, other polymerizable monomers may be included within the scope not departing from the gist of the present invention. Other polymerizable monomers include (meth) acrylates that do not have a carbocyclic skeleton.

(Polymerization initiator)
In this invention, when using a photoinitiator, it is preferable that the content in a polymeric composition is 0.1 mol% or more of the total amount of a polymeric compound, and is 0.5-2 mol%. Is more preferable. 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 (for example, Darocur TPO, Darocur 1173, etc.), and Ezacure series (for example, Ezacure TZM, Ezacure TZT, Ezacure KTO46, etc.) commercially available from Lamberti. Can be mentioned.

(Formation method of organic layer)
A method for forming the organic layer is not particularly defined, but for example, 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 vapor deposition 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. Since (meth) acrylates used in the present invention 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, 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 polymerization rate of the polymerizable monomer constituting the organic layer is preferably 85% or more, more preferably 88% or more, further preferably 90% or more, and particularly preferably 92% or more. . The polymerization rate here means the ratio of the reacted polymerizable group among all the polymerizable groups (for example, acryloyl group and methacryloyl group) in the polymerizable composition. 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 1 nm or less, and more preferably 0.5 nm or less, 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.

(Inorganic layer)
The inorganic layer is usually a thin film layer made of a metal compound. In the present invention, the inorganic layer is formed by a plasma assisted vapor deposition method. Here, the plasma assisted vapor deposition method refers to a method of performing vapor deposition while ionizing a vapor deposition material by plasma during vacuum vapor deposition, or irradiating gas ions from an ion source provided separately.
Ordinary vacuum deposition is less advantageous in strength and density of the film because the energy of the flying particles is smaller than that of a thin film in sputtering or the like. On the other hand, by performing plasma assist, the deposition material obtains energy, so that a thin film having high strength and density can be formed even in vacuum deposition. In addition, since the excited species in plasma are rich in reactivity, a thin film can be formed by arbitrarily oxidizing, nitriding, and carbonizing the evaporation source by introducing a gas such as oxygen, nitrogen, acetylene, or the like.
By providing an inorganic layer by such a method, the film can be formed faster than sputtering or plasma CVD. In the present invention, a resin having a carbon cyclic skeleton is used for the organic layer, and it is difficult to be damaged by plasma, and by using plasma assist, a dense inorganic layer is formed and the barrier property is kept high. Is.
In the present invention, the plasma assist is preferably performed at an ion current density of 30 to 300 μA / cm ² , and more preferably 60 to 120 μA / cm ² . Moreover, it is preferable that it is 100-5000V, and, as for an ion assist voltage, it is more preferable that it is 200-1000V.
Examples of the gas used for plasma assist include argon gas, oxygen gas, nitrogen gas, and acetylene gas. Moreover, these mixed gas may be sufficient. In the present invention, argon gas, oxygen gas, or a mixed gas thereof is preferable.

The component contained in the inorganic layer is not particularly limited as long as it does not depart from the gist of the present invention. For example, it is a metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide, and Si, Al, In An oxide, nitride, carbide, oxynitride or oxycarbide containing one or more metals selected from Sn, Zn, Ti, Cu, Ce and Ta can be preferably used. Among these, 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. In the present invention, preferred examples include silicon oxide represented by the chemical formula SiOx and x being 0.9 to 1.5. This kind of inorganic layer is colored, so it was not used in an organic EL element or the like. However, when used in a solar cell, coloring is not a problem.
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.

(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. During the production of the barrier laminate, 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.

(Functional layer)
The device of the present invention may have a functional layer 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, 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.

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. The support includes various devices in addition to the base film. Preferably, the barrier laminate of the present invention can be used as a barrier layer of a gas barrier film. 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. FIG. 1 shows an example of a gas barrier film according to the present invention, and a barrier laminate comprising an organic layer 2 and an inorganic layer 3 is laminated on a base film 1. In the conventional gas barrier film, since the inorganic layer was formed by sputtering or plasma CVD method, it was recognized that the organic layer as the underlayer was damaged, but in the present invention, the plasma assist deposition method is adopted. This makes it difficult to receive damage. In addition, a dense inorganic layer can be formed by using a plasma assist vapor deposition method.
As shown in FIG. 2, the gas barrier film may further include a plurality of organic layers 2 and inorganic layers 3 on the base film 1. Further, although not shown, an organic layer and an inorganic layer may be provided on both surfaces of the base film. Moreover, contrary to FIG. 2, you may laminate | stack in order of the inorganic layer, the organic layer, the inorganic layer, and the organic layer from the base film side. In this case, it is preferable to form the inorganic layer provided on the surface of the organic layer by a plasma assisted vapor deposition method.
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 barrier 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 for applications requiring heat resistance, the base 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 as a sheet or the like on the front side of a solar cell element, the base film is transparent, that is, the light transmittance is usually 80% or more, preferably 85% or more, more preferably. Is 90% or more. 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.

  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. As for the functional layer, in addition to those described above, those described in paragraph numbers 0036 to 0038 of JP-A-2006-289627 can be preferably employed.

<Composite film>
In the present invention, two of the above gas barrier films may be used as a composite film having a structure in which two sheets are bonded together with the barrier laminate on the inside. By bonding two gas barrier films, the barrier property can be further enhanced. FIG. 3 shows an example in which two gas barrier films are bonded, and the gas barrier film in which the organic layer 2 and the inorganic layer 3 are provided on the base film 1 is interposed through the adhesive layer 4. Are pasted together. Furthermore, a gas barrier film can also be bonded to such a composite film.
The adhesive layer is a layer mainly composed of an adhesive, and usually 70% by weight or more of the adhesive layer is an adhesive, and preferably 80 to 90% by weight of the adhesive layer is an adhesive. . As the adhesive, known adhesives can be widely used, but a urethane adhesive is preferable. Here, examples of the urethane-based adhesive include a thermosetting type and an ultraviolet curable type. When the barrier film absorbs ultraviolet rays, a thermosetting type is preferable. Among thermosetting types, there are a one-component type and a two-component mixed type. In the present invention, an adhesive that becomes colorless and transparent after curing is preferred. Examples of commercially available products include Seika Bond E series manufactured by Dainichi Seika, DIC, and Dick Dry LX series.
Furthermore, it is also preferable to add a silane coupling agent to the adhesive. By adding a silane coupling agent, the adhesive force can be increased more effectively.

<Device>
The barrier laminate, gas barrier film and composite film of the present invention can be preferably used for devices whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. In particular, the barrier laminate, gas barrier film and composite film of the present invention are preferably used for electronic paper and solar cell sheets, and more preferably for solar cell sheets.

(Solar cell)
The gas barrier film of the present invention can be used as a sheet for solar cells. The solar cell element usually has a configuration in which an active portion that functions as a solar cell is provided between a pair of substrates. The gas barrier film or the composite film of the present invention is used as one or both of the pair of substrates. Can do.
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).

(Electronic paper)
The gas barrier film of the present invention can also be used for electronic paper. Electronic paper is a reflective electronic display, and can achieve high definition and a high contrast ratio.
Electronic paper has a display medium and a TFT for driving the display medium on a substrate. Any conventionally known display medium can be used as the display medium. Any display medium such as an electrophoretic method, an electronic powder particle flying method, a charged toner method, and an electrochromic method is preferably used, but an electrophoretic display medium is more preferable, and in particular, a microcapsule type electrophoresis. A display medium of the type is particularly preferred. An electrophoretic display medium is a display medium that includes a plurality of capsules, each of the plurality of capsules including at least one particle that is movable within the suspending fluid. The at least one particle referred to here is preferably an electrophoretic particle or a rotating ball. In addition, the electrophoretic display medium has a first surface and a second surface facing the first surface, and is observed through one of the first and second surfaces. Display an image.
Further, the TFT provided on the substrate has at least a gate electrode, a gate insulating film, an active layer, a source electrode, and a drain electrode, and at least one between the active layer and the source electrode or between the active layer and the drain electrode. It further has a resistance layer to be electrically connected. Electronic paper produces light shading when a voltage is applied.

  When manufacturing an electronic display with high-definition color display, it is preferable to form TFTs on a color filter in order to ensure alignment accuracy. However, there is a limit to downsizing even if a required driving current is obtained with a normal TFT having low current efficiency, and the area occupied by the TFT in the pixel becomes larger as the display medium becomes higher in definition. As the area occupied by the TFT in the pixel increases, the aperture ratio decreases and the contrast ratio decreases. For this reason, even if a transparent amorphous IGZO TFT is used, the light transmittance is not 100%, and a reduction in contrast is inevitable. Therefore, for example, by using a TFT as described in Japanese Patent Application Laid-Open No. 2009-021554, the area occupied by the TFT in the pixel can be reduced and the aperture ratio and the contrast ratio can be increased. Further, if this type of TFT is formed directly on the color filter, high definition can be achieved.

(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., and described in JP-A-2002-865554. And an organic EL device described in JP-A-2007-30387 can be preferably 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.

Creation of gas barrier film (1)
A PET film (Cosmo Shine A4300, 100 μm thick) was cut into a 10 cm square, and an organic layer and an inorganic layer were formed on the surface by the following procedure and evaluated.

(Create organic layer)
A polymerizable composition comprising a polymerizable compound having the composition shown in the following table on the PET film, 0.6 g of an ultraviolet polymerization initiator (Ciba Specialty Chemicals, Ciba Irgacure 184), and 190 g of propylene glycol monomethyl ether acetate, It is applied using a wire bar, and the organic layer is cured by irradiating ultraviolet rays from a high-pressure mercury lamp (accumulated dose of 1.5 J / cm ² ) with an oxygen concentration of 0.1% or less by a nitrogen substitution method. An organic layer of about 1 μm was formed. When applying Compound F and PMMA, they were applied without adding an ultraviolet polymerization initiator, and then dried at 80 ° C. for 5 minutes.
(Creation of inorganic layer)
An inorganic layer is formed on the organic layer using an EB + ion gun type plasma-assisted deposition apparatus (Shincron, ACE1350IAD) under the conditions of ion assist voltage: 900 V, oxygen gas flow rate: 50 sccm, argon gas flow rate: 8 sccm. Was deposited using SiO as a deposition source while using oxygen plasma assist. The thickness of the inorganic layer was 50 nm. The film forming speed was 5 nm / sec. The film forming speed when the film is formed by the sputtering method is 0.1 nm / sec, and it can be seen that the film forming speed is extremely high in the method of the present invention.

Measurement of water vapor transmission rate by Mocon method The obtained gas barrier film was measured using “PERMATRAN-W3 / 31” (40 ° C., relative humidity 90%) manufactured by MOCON. The results are shown in the table below.

Preparation of gas barrier film (comparative example) (2)
As a comparative example, in the preparation of the gas barrier film (1), the kind of the compound used for forming the organic layer is replaced with the one described in the following table, and the inorganic layer is formed in the same manner as described above or with an ion assist voltage of 0 V The water vapor transmission rate was measured. The results are shown in the table below.

The above compounds are as follows.

Compound A: Shin Nakamura Chemical Co., Ltd., NK Oligo EA-1020
Compound B: Shin-Nakamura Chemical Co., Ltd., NK ester A-BPEF
Compound C: Shin Nakamura Chemical Co., Ltd., NK Oligo EA-6320
Daicel Cytec, TPGDA
Compound D: Daicel Cytec, IRR214-K
Compound F: Aldrich, Polystyrene average, weight average molecular weight 200000
Compound G: Kyoeisha Chemical Co., Ltd., light acrylate BEPG-A
Compound H: Methyl acrylate, manufactured by Aldrich
PMMA (polymethyl methacrylate): Aldrich: Poly (methyl methacrylate), weight average molecular weight 120,000 or less (GPC), powder)

Creation of gas barrier film (3)
It was found that when Al ₂ O ₃ was used instead of SiO in the gas barrier film preparation (1), the same tendency was shown.

Creation of gas barrier film (4)
In preparation (1) of the above gas barrier film, an organic layer and an inorganic layer were further formed in the same manner to prepare a multilayer gas barrier film. The gas barrier property of the obtained gas barrier film was measured by the above method. The results are shown below.

Creation of gas barrier film (5)
In the preparation of the gas barrier film (1), the formation conditions of the inorganic layer were changed to ion assist voltage: 450 V, oxygen gas flow rate: 50 sccm, and argon gas flow rate: 8 sccm, and the others were performed in the same manner. The gas barrier property of the obtained gas barrier film was measured by the above method. The results are shown below.

Creation of gas barrier film (6)
The barrier laminates of the gas barrier film prepared in the preparation (1) of the gas barrier film were bonded together with an adhesive (manufactured by Dainichi Seika Co., Ltd., main agent: E-372, curing agent: C-76). The gas barrier property of the obtained composite film was measured by the above method. The results are shown below.

Creation of Solar Cell A solar cell module was created using the gas barrier film created with the gas barrier film (6). Specifically, a standard cure type ethylene-vinyl acetate copolymer was used as a filler for the solar cell module. A solar cell module was prepared by sandwiching and filling amorphous silicon solar cells with an ethylene-vinyl acetate copolymer having a thickness of 450 μm on a 10 cm square tempered glass and further installing a gas barrier film thereon. As installation conditions, vacuuming was performed at 150 ° C. for 3 minutes, and then pressure bonding was performed for 9 minutes. The solar cell module produced by this method operated well and exhibited good electrical output characteristics even in an environment of 85 ° C. and 85% relative humidity.

1 Base film 2 Organic layer 3 Inorganic layer 4 Adhesive layer

Claims (9)

A base film, and a barrier laminate comprising an organic layer and an inorganic layer, wherein the organic layer has the following formula on the base film :

Is a layer obtained by applying and curing a polymerizable composition containing a polyfunctional (meth) acrylate represented by formula (II) and a polymerization initiator, and the inorganic layer is formed on the surface of the organic layer by a plasma-assisted vapor deposition method. A gas barrier film characterized by being a layer. The gas barrier film according to claim 1 , wherein the inorganic layer contains silicon and / or aluminum. The gas barrier film according to claim 1 or 2 , wherein the plasma used for forming the inorganic layer is argon gas, oxygen gas, or a mixed gas thereof. The gas barrier film according to any one of claims 1 to 3, wherein the barrier laminate is formed by alternately laminating at least two organic layers and at least two inorganic layers. A composite film having a structure in which two gas barrier films according to any one of claims 1 to 4 are bonded with the barrier laminate side facing inward. The member for solar cells containing the gas barrier film of any one of Claims 1-4 . The member for solar cells containing the composite film of Claim 5 . A method for producing a gas barrier film comprising a substrate film and a barrier laminate comprising an organic layer and an inorganic layer, wherein the following formula:

The inorganic layer is formed by applying and curing a polymerizable composition containing a polyfunctional (meth) acrylate represented by formula (II) and a polymerization initiator to form the organic layer, and plasma assisted deposition on the surface of the organic layer. The manufacturing method including forming. The manufacturing method according to claim 8 , wherein the curing is curing with ultraviolet rays.

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