WO2011027902A1

WO2011027902A1 - Barrier laminate, gas barrier film and method for manufacturing the barrier laminate

Info

Publication number: WO2011027902A1
Application number: PCT/JP2010/065358
Authority: WO
Inventors: Ryou Oouchi; Shigehide Itou
Original assignee: Fujifilm Corporation
Priority date: 2009-09-01
Filing date: 2010-09-01
Publication date: 2011-03-10
Also published as: JP2011051194A; JP5580561B2

Abstract

Provided is a barrier laminate which can be formed at a fast speed and which is excellent in barrier property thereof. Disclosed is a barrier laminate, comprising at least one organic layer and at least one inorganic layer, wherein the organic layer comprises a resin having a cyclic skeleton consisting of carbon atoms, and the inorganic layer is formed by plasma-assisted deposition method.

Description

DESCRIPTION

BARRIER LAMINATE, GAS BARRIER FILM AND METHOD FOR MANUFACTURING THE BARRIER LAMINATE

TECHNICAL FIELD

The invention relates a novel barrier laminate, a gas barrier film, a method for manufacturing a barrier laminate. In particular, the invention relates to a gas barrier film favorably used for solar cell members.

BACKGROUND ART

Heretofore, a film capable of shutting water vapor or oxygen, so-called a film having gas barrier property (gas barrier film) has been investigated. JP-A-8-165368 discloses that the inorganic layer is formed by sputtering method or plasma CVD method for the purpose of enhancing the gas barrier property of the gas barrier film.

Gas barrier films have been used for various applications, and, in recent years, they are used for a sheet for sealing a solar cell, or an electronic paper (JP-A-2009-49252 ) . In the case where the gas barrier film is used for a solar cell, or the like, the gas barrier film having a relatively large area is demanded, so that the gas barrier film is required to increase its productivity such as formation speed or cost. Heretofore, enhancement of the barrier property of the gas barrier films has been investigated. However, enhancement of the productivity of the gas barrier film has not sufficiently been investigated. SUMMARY OF THE INVENTION

Such purpose for enhancing the barrier property of the gas barrier film is achieved by forming the inorganic layer according to sputtering method or a plasma CVD method. However, both methods are impractical in the case where the gas barrier film having a large-area is required. This is because the sputtering method is remarkably slow in its formation speed and the plasma CDV method is expensive in its cost. The object of the invention is to provide a barrier laminate which has a large area, of which the inorganic layer can be formed at high productivity without using the sputtering method or CDV method and which has high barrier property. The object of the invention is also to provide a gas barrier film comprising such a barrier laminate.

Under such situation, in order to form the inorganic layer according to a method capable of forming it at a faster rate than that in the sputtering method or CVD method, the inventor has tried to form the inorganic layer by using plasma-assisted deposition method. However, it was found that, when the plasma-assisted deposition method is merely used, an organic layer which serves as the underlayer of the inorganic layer suffers damage caused by plasma. The inventors further investigated and found that such trouble can be resolved by using a resin having a cyclic carbon skeleton as a material constituting the organic layer, and thereby accomplished the invention. Specifically, they found that the above objection can be solved by the following means.

[1] A barrier laminate comprising at least one organic layer and at least one inorganic layer, wherein the organic layer comprises a resin having a cyclic skeleton consisting of carbon atoms, and the inorganic layer is formed by plasma-assisted deposition method.

[2] The barrier laminate according to [1], wherein the resin in the organic layer is an ultraviolet curable resin.

[3] The barrier laminate according to [1] or [2], wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a (meth) acrylate having a cyclic skeleton consisting of carbon atoms.

[4] The barrier laminate according to any one of [1] to [3], wherein the inorganic layer comprises silicon and/or aluminium.

[5] The barrier laminate according to any one of [1] to [4], wherein the inorganic layer is formed by using gas selected from argon gas, oxygen gas and a mixture thereof.

[6] The barrier laminate according to any one of [1] to [5] , which comprises at least two organic layers and at least two inorganic layers laminated alternately.

[7] The barrier laminate according to any one of [1] to [6], wherein the resin in the organic layer is obtained by curing a polymerizable composition comprising a (meth) acrylate having an aromatic ring.

[8] The barrier laminate according to any one of [1] to [6], wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a polyfunctional (meth) acrylate .

[9] The barrier laminate according to any one of [1] to [6] , wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a polyfunctional (meth) acrylate having an aromatic ring.

[10] The barrier laminate according to any one of [1] to [6], wherein the cyclic skeleton consisting of carbon atoms is selected from benzene 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, perylene skeleton, and benzopyrene skeleton.

[11] The barrier laminate according to any one of [1] to [5] , wherein the resin in the organic layer is obtained by curing a polymerizable composition comprising at least one kind of the following compounds:

[12] The barrier laminate according to any one of [1] to [11] , wherein the plasma-assisted deposition method is carried out at an ion current density of 30 to 300 μΑ/cm², and at an ion-assisted voltage of 100 to 5000V.

[13] The barrier laminate according to any one of [1] to [12] , wherein the organic layer has a thickness of 50 to 2000 nm and the inorganic layer has a thickness of 5 to 500 nm.

[14] A gas barrier film comprising a substrate and the barrier laminate of any one of [1] to [13] on the substrate. [15] A composite film comprising two gas barrier films, wherein the gas barrier films each are the gas barrier film of [14] and are stuck to each other on a side of the barrier laminate.

[16] A member for a solar cell, comprising the gas barrier film of [14] , or the composite film of [15] .

[17] A method for manufacturing a barrier laminate comprising an organic layer and an inorganic layer, wherein the organic layer comprises a resin comprising having a cyclic skeleton consisting of carbon atoms; and

which comprises forming the inorganic layer by plasma-assisted deposition method.

[18] The method for manufacturing the barrier laminate according to [17], which further comprises forming the organic layer by curing a polymerizable composition comprising a (meth) acrylate having an aromatic ring.

[19] The method for manufacturing the barrier laminate according to [17] or [18], wherein the plasma-assisted deposition method is carried out at an ion current density of 30 to 300 μΑ/cm², and at an ion-assisted voltage of 100 to 5000V.

[20] The method for manufacturing the barrier laminate according to any one of [17] to [19], wherein the inorganic layer is formed in a clean room at the degree of cleanness of at most class 10000.

[21] The method for manufacturing the barrier laminate according to any one of [17] to [20], wherein the barrier laminate is the barrier laminate of any one of [1] to [13] .

The invention makes it possible to form a barrier laminate and a gas barrier film which have high barrier property at high production speed. Therefore, the barrier laminate and the gas barrier film are preferably used in the case of using great quantity of the gas barrier film such as a sheet for a solar cell.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 shows an example of preferable embodiment of the gas barrier film of the invention.

Fig. 2 shows another example of preferable embodiment of the gas barrier film of the invention.

Fig. 3 shows an example of preferable embodiment of the composite film of the invention.

In the Figures, 1 stands for a substrate film, 2 stands for an organic layer, 3 stands for an inorganic layer and 4 stands for an adhesive layer.

DETAILED DESCRIPTION OF INVENTION

The contents of the invention are described in detail hereinunder. In this description, the numerical range expressed by the wording "a number to another number" means the range that falls between the former number indicating the lowermost limit of the range and the latter number indicating the uppermost limit thereof. "Organic EL device" as referred to herein means an organic electroluminescent device. In addition,

" (meth) acrylate" means acrylate and methacrylate in the present specification.

The barrier laminate of the invention comprises at least one organic layer and at least one inorganic layer, preferably has a structure in which the inorganic layer is formed on the surface of the organic layer, and more preferably has a structure in which at least two organic layers and at least two inorganic layers are alternately laminated.

Numbers of the layers constituting the barrier laminate of the invention is not specifically limited, and preferably 2 to 30, more preferably 3 to 20. The barrier laminate may comprise one or more other layers than the organic layer and the inorganic layer .

(Organic Layer)

The organic layer comprises a resin comprising a cyclic skeleton consisting of carbon atoms. Examples of the carbon cyclic sklelton include benzene 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, perylene skeleton, and benzopyrene skeleton. The cyclic skeleton consisting of carbon atoms in the invention preferably comprises one or more aromatic rings. More preferably, the organic layer of the invention comprises a resin obtained by curing a polymerizable composition comprising a polymerizable compound having one or more aromatic rings. By using the resin comprising a cyclic skeleton consisting of carbon atoms comprising one or more aromatic rings, the layer to be formed is resistant to decomposition even during plasma process. As a result, the barrier property tends to be enhanced.

The resin contained in the organic layer in the invention is preferably a resin having a three dimensional cross-linking property. By using such a resin, the organic layer to be formed has more dense structure.

The resin used in the organic layer of the invention is preferably an ultraviolet curable resin, preferably a resin obtained by curing a polymerizable composition comprising a (meth) acrylate comprising a cyclic skeleton consisting of carbon atoms, particularly preferably a resin obtained by curing a polymerizable composition comprising a (meth) acrylate comprising an aromatic ring. Using such a resin can promptly form a cured film. The (meth) acrylate may be monofunctional or polyfunctional, preferably polyfunctional . Use of such a polyfunctional (meth) acrylate makes it possible to construct a three dimensional cross-linking structure in the organic layer to be formed.

The (meth) acrylates preferably used in the invention are exemplified below, to which, however, the invention is not limited thereto.

The organic layer in the invention is preferably obtained by curing a polymerizable composition comprising a polymerizable compound as mentioned above and a polymerization initiator. The content of a (meth) acrylate having an aromatic carbon skeleton is preferably 50 to 100% by weight, relative to the polymerizable compound ingredient in the polymerizable composition.

The polymerizable composition may comprise a polymerizable monomer in addition to the above polymerizable compounds without diverting the scope of the invention. The other polymerizable monomer is exemplified by a (meth) acrylate not having an aromatic carbon skeleton.

(Polymerization Initiator)

In the case where a photopolymerization initiator is used in the invention, its amount is preferably at least 0.1 mol% of the total amount of the polymerizing compound, more preferably from 0.5 to 2 mol%. By setting the thus-designed composition, polymerization reaction though an active ingredient forming reaction may be suitably controlled. Examples of the photopolymerization initiator include Ciba Speciality Chemicals' commercial products, Irgacure series (e.g., Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 819) , Darocure series (e.g., Darocure TPO, Darocure 1173), Quantacure PDO; Lamberti's commercial products, Ezacure series (e.g., Ezacure TZM, Ezacure TZT, Ezacure KT046) , etc.

(Method of formation of organic layer)

The method for forming the organic layer is not specifically defined. For example, the layer may be formed according to a solution coating method or a vacuum film formation method. The solution coating method is, for example, a dipping 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 an extrusion coating method using a hopper as in USP 2681294. The vacuum film formation method is not specifically defined, but is preferably a film formation method by vapor deposition or plasma CVD, and the like. In the invention, the polymer may be applied for coating as its solution, or a hybrid coating method along with an inorganic material, as in JP-A 2000-323273 and 2004-25732, may also be used.

In the invention, the composition comprising the polymerizable monomer is generally cured by irradiation. The light for irradiation is generally a UV ray from a high-pressure mercury lamp or low-pressure mercury lamp. The radiation energy is preferably at least 0.1 J/cm², more preferably at least 0.5 J/cm². (Meth) acrylate series compounds used in the invention may suffer from interference in polymerization owing to oxygen in air, and therefore, in their polymerization, the oxygen concentration or the oxygen partial pressure is preferably lowered. In the case where the oxygen concentration in polymerization is lowered according to a nitrogen purging method, the oxygen concentration is preferably not more than 2 %, more preferably not more than 0.5 %. In the case where the oxygen partial pressure in polymerization is lowered by a pressure reduction method, the whole pressure is preferably not more than 1000 Pa, more preferably not more than 100 Pa. Especially preferred is UV polymerization with at least 0.5 J/cm² energy radiation under a condition of reduced pressure of not more than 100 Pa.

The organic layer in the invention preferably is smooth and has high film hardness. Preferably, the rate of polymerization of monomer is at least 85%, more preferably at least 88%, even more preferably at least 90%, still more preferably at least 92%. The rate of polymerization as referred to herein means the ratio of the reacted polymerizable group to all the polymerizing group (acryloyl group and methacryloyl group) in the monomer mixture. The rate of polymerization may be quantitatively determined according to IR absorptiometry.

The thickness of the organic layer is not specifically defined. However, when the layer is too thin, then its thickness could hardly keep uniformity; but when too thick, the layer may be cracked by external force applied thereto and its barrier property may lower. From these viewpoints, the thickness of the organic layer is preferably from 50 nm to 2000 nm, more preferably from 200 nm to 1500 nm.

As so mentioned in the above, the organic layer is preferably smooth. The mean roughness (Ra) in 1 μιη square is preferably not more than 1 nm, more preferably not more than 0.5 nm. The surface of the organic layer is required not to have impurities and projections such as particles. Accordingly, it is desirable that the organic layer is formed in a clean room. The degree of cleanness is preferably not more than class 10000, more preferably not more than class 1000.

Generally preferably the hardness of the organic layer is higher. When the higher the hardness of the organic layer is, the more smooth the inorganic layer to be formed is. As a result, the barrier property is enhanced. The hardness of the organic layer may be expressed as an icrohardness based on a nano-indentation method. The microhardness of the organic layer is preferably at least 100 N/mm, more preferably at least 150 N/mm. (Inorganic Layer)

The inorganic layer is, in general, a layer of a thin film formed of a metal compound. The inorganic layer in the invention is formed by plasma-assisted deposition method. The plasma-assisted deposition method is deposited by ionizing material to be deposited by plasma during vacuum deposition, or by irradiating gas ion from ion source separately prepared during vacuum deposition.

The common vapor deposition methods are not advantageous for strength and density of the obtained film because discharging particles in the common vapor deposition methods have smaller energy than those in a sputtering method. On the other hand, the plasma-assisted deposition method can produce a thin film having excellent strength and high density because the deposition material obtains energy by carrying plasma-assisting. In addition, an arbitrarily oxygenized, nitrided, or carbonized film can be obtained by introducing a gas such as oxygen, nitrogen, or acethylene, since the excited materials during the plasma process are highly-reactive.

By forming the inorganic layer according to such plasma-assisted deposition method, the film formation can be attained faster than by a sputtering method or a plasma CVD method. The invention uses a resin having a cyclic skeleton consisting of carbon atoms as a material of the organic layer to thereby reduce the damage based on plasma and forms the dense inorganic layer by the plasma-assisted deposition method, and thereby, the invention successfully achieved maintaining high barrier property of the gas barrier film.

In the invention, the plasma-assisted deposition method is preferably carried out at an ion current density of 30 to 300 μΑ/cm², more preferably 60 to 120 μΑ/cm². The ion-assisted voltage is preferably 100 to 5000V, and more preferably 200 to 1000 V. Examples of gas used for the plasma-assisted deposition method include argon gas, oxygen gas, nitrogen gas, and acethylene gas. The gas may be a mixture thereof. In the invention, argon gas, oxygen gas and the mixture thereof are preferable.

Not specifically defined, the component to be in the inorganic layer may be any one without diverting the scope of the invention. For example, it includes metal oxides, metal nitrides, metal carbides, metal oxinitrides, or metal oxicarbides, and is preferably oxides, nitrides, carbides, oxinitrides, or oxicarbides containing at least one metal selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta. Of those, preferred are oxides, nitrides, carbides, oxicarbides, or oxinitrides of a metal selected from Si, Al, In, Sn, Zn and Ti; more preferred are metal oxides, nitrides or oxinitrides with Si or Al . These may contain any other element as a subsidiary component. In the invention, one of preferable examples is silicon oxide represented by SiOx, wherein x is 0.9 to 1.5. While such an inorganic layer isn't used for an organic EL device because of its coloration, the coloration is not a problem in the case of using a solar cell.

Surface smoothness of the inorganic layer formed in the invention is less than 1 nm in terms of the mean roughness (Ra value) in 10 μπι square, more preferably at most 0.5 nm. It is desirable that the inorganic layer is formed in a clean room. Preferably, the degree of cleanness is at most class 10000, more preferably at most class 1000.

The thickness of the inorganic layer is not specifically limited, in general 5 to 500nm per layer, and preferably 10 to 200nm per layer. The inorganic layer may be a laminate structure composed of multiple sub-layers. In such a case, each of the sub-layers may have the same composition or different composition to each other.

(Lamination of Organic Layer and Inorganic Layer)

The barrier laminate of the organic layer and the inorganic layer is formed by repeatedly and sequentially forming the organic layers and the inorganic layers in accordance with a desired structure. During the formation of the barrier laminate, the lamination of the organic layer and the inorganic layer is particularly preferably carried out in vacuum at 1000 Pa or less without returning the pressure to atmosphere pressure. The pressure is preferably 100 Pa or less, more preferably 50 Pa or less, further preferably 20 Pa or less.

(Functional Layer)

The functional layer may be provided on the barrier laminate or on other positions in a device of the invention. The functional layer is described in detail in JP-A 2006-289627, paragraphs 0036 to 0038. Examples of other functional layers than those include a matting agent layer, a protective layer, a solvent resistance layer, an antistatic layer, a planarizing layer, an adhesiveness improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxing layer, an antifogging layer, an anti-soiling layer, a printable layer, an easy adhesive layer, etc.

Use of Barrier Laminate

The barrier laminate of the invention is generally provided on a support, and can be used for various applications by selecting the support. The support includes various devices in addition to a substrate film. Preferably, the barrier laminate of the invention is used as a barrier layer of a gas barrier film. The details are described below.

The gas barrier film has a substrate film and the barrier laminate on the substrate film. Fig 1. shows an example of the gas barrier film of the invention, wherein the barrier laminate consisting one organic layer 2 and one inorganic layer 3 is provided on the surface of the substrate film 1. The inorganic layer in the conventional gas barrier film was formed by a sputtering method or a plasma CDV method, so that the organic layer which is the underlayer of the inorganic layer was sometimes damaged. The invention, however, uses plasma-assisted deposition method, so that the organic layer can be less to damage . The invention also can form a dense inorganic layer by using the plasma-assisted deposition method.

In the gas barrier film, a plurality of organic layers 2 and a plurality of inorganic layers 3 may be formed on the substrate film 1 as shown in Fig. 2. Although it is not shown in a figure, the organic layer and the inorganic layer may be formed on the both surface of the substrate film. Also, contrary to Fig. 2, an inorganic layer, an organic layer, an inorganic layer and an organic layer may be laminated on the substrate film in that order. In such a case, the inorganic layer to be formed on the organic layer is preferably formed by the plasma-assisted deposition method.

Numbers of the layers constituting the gas barrier film is not specifically limited. It is typically 2 to 30, and preferably 3 to 20.

The gas barrier film may comprise another layer other than the barrier substrate and substrate film, for example, a functional layer such as an easy adhesive layer.

(Plastic Film)

In the gas barrier film in the invention, the substrate film is generally a plastic film. Not specifically defined in point of the material and the thickness thereof, the plastic film usable herein may be any one capable of supporting a laminate film of an organic layer and an inorganic layer; and it may be suitably selected depending on the use and the object thereof. Concretely, the plastic film includes thermoplastic resins such as polyester resin, methacryl resin, methacrylic acid-maleic anhydride copolymer, polystyrene resin, transparent fluororesin, polyimide, fluoropolyimide resin, polyamide resin, polyamidimide resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic-modified polycarbonate resin, fluorene ring-modified polyester resin, acryloyl compound.

In case where the gas barrier film of the invention is used for an application requesting heat-resistance, it is desirable that the plastic film is formed of a heat-resistant material. Concretely, the plastic film is preferably formed of a heat-resistant transparent material having a glass transition temperature (Tg) of not lower than 100°C and/or a linear thermal expansion coefficient of not less than 40 ppm/°C. Tg and the linear expansion coefficient may be controlled by the additives to the material. The thermoplastic resin of the type includes, for example, polyethylene naphthalate (PEN: 120°C) , polycarbonate (PC: 140°C) , alicyclic polyolefin (e.g., Nippon Zeon's Zeonoa 1600: 160°C) , polyarylate (PAr: 210°C) , polyether sulfone (PES: 220°C) , polysulfone (PSF: 190°C) , cycloolefin copolymer (COC, compound described in JP-A 2001-150584 : 162°C) , polyimide (Mitsubishi gas chemical company's Neopulim : 260 °C) , fluorene ring-modified polycarbonate (BCF-PC, compound described in JP-A 2000-227603: 225°C) , alicyclic-modified polycarbonate (IP-PC, compound described in JP-A 2000-227603: 205°C) , acryloyl compound (compound described in JP-A 2002-80616 : 300°C or more) (the parenthesized data are Tg) . In particular, for high transparency, use of alicyclic polyolefin is preferred.

In view of the matter that the gas barrier film of the invention is utilized as a device such as solar cells, the plastic film must be transparent, namely its light transmittance is usually not less than 80%, preferably not less than 85%, and more preferably not less than 90%. The light transmittance can be measured by a method described in JIS-K7105, namely by measuring a total light transmittance and an amount of scattered light using an integrating sphere type light transmittance analyzer and subtracting the diffuse transmittance from the total light transmittance .

The thickness of the plastic film to be used for the gas barrier film of the invention is properly chosen depending upon the use and therefore, is not particularly limited. It is typically from 1 to 800 urn, and preferably from 10 to 200 jam. These plastic films may have a functional layer such as a transparent conductive layer and a primer layer. The functional layer is described in detail in paragraphs 0036 to 0038 of JP-A-2006-289627.

The invention also relates to a composite film, wherein the above gas barrier films are stuck so that the barrier laminate sides are faced to each other. By sticking the two gas barrier films, the barrier property thereof can be enhanced. Fig. 3 shows an example that two gas barrier films are stuck to each other, wherein the gas barrier films consisting of the organic layer 2 and the inorganic layer 3 on the substrate film 1 are stuck to each other through the adhesive layer 4. Such a composite film may be further stuck to the gas barrier film.

The adhesive layer is a layer comprising an adhesive as a main ingredient, wherein the adhesive generally occupies 70% by weight of the adhesive layer, preferably 80 to 90% by weight of the adhesive layer. Various known adhesives may be used as the adhesive, and preferably a urethane series adhesive. The urethane series adhesive is exemplified by a thermal curing adhesive and a UV curing adhesive. In the case where the laminate film can absorb UV, the thermal curing adhesive is preferable. The thermal curing adhesive includes one liquid type and two liquids type, and both types are preferably used in the invention. In the invention, an adhesive which becomes transparent after cured is preferable. Examples of the commercial adhesive include Seika bond E series manufactured by Dainichiseika Color & Chemicals and DICDRY LX series manufactured by DIC. In addition, a silane coupling agent is preferably added into the adhesive. By adding the silane coupling agent, the adhesion force is effectively enhanced.

The barrier laminate and the gas barrier film of the invention are favorably used for devices that are deteriorated by the chemical components in air (e.g., oxygen, water, nitrogen oxide, sulfur oxide, ozone) . The barrier laminate and the gas barrier film of the invention are more preferably used for an electronic paper and a sheet for a solar cell, further more preferably a sheet for a solar cell.

(Solar Cell)

The gas barrier film of the invention can be used as a sheet for a solar cell. The solar cell generally has an active part which practically operates as a solar cell between a pair of substrates. In the invention, the gas barrier film or composite film of the invention may be used as one or both of the pair of substrates .

The solar cell for which the gas barrier film of the invention is favorably used is not specifically defined. For example, they include single crystal silicon-based solar cell devices, polycrystalline silicon-based solar cell devices, single-junction or tandem-structure amorphous silicon-based solar cell devices, gallium-arsenic (GaAs) , indium-phosphorus (InP) or the like III-V Group compound semiconductor-based solar cell devices, cadmium-tellurium (CdTe) or the like II-VI Group compound semiconductor-based solar cell devices, copper/indium/selenium (CIS-based) , copper/indium/gallium/selenium (CIGS-based) , copper/indium/gallium/selenium/sulfur (CIGSS-based) or the like I-III-VI Group compound semiconductor-based solar cell devices, dye-sensitized solar cell devices, organic solar cell devices, etc. Above all, in the invention, the solar cell devices are preferably copper/indium/selenium (CIS-based), copper/indium/gallium/selenium (CIGS-based) , copper/indium/gallium/selenium/sulfur (CIGSS-based) or the like I-III-VI Group compound semiconductor-based solar cell devices. (Electronic paper)

The gas barrier film of the invention can be used in an electronic paper. The electronic paper is a reflection-type electronic display capable of attaining a high precision and a high contrast.

The electronic paper has a display media and a TFT driving the display media on a substrate. Any known display media can be used in the electronic paper. For example, any display media of electophoretic-type, electopowder flight-type, charged tonner-type, electrochromic type can be preferably used. Among them, electophoretic display media is more preferable and microcapsule-type electophoretic display media is particularly preferable. The electophoretic display media has a plural number of capsules and each capsule has at least one particle capable of moving in a suspension flow. The at least one particle is preferably an electrophoretic particle or a spinning ball. The electrophretic display media has a first plane and a second plane that are placed in parallel, and an image is displayed through one of the two planes.

A TFT formed on a substrate comprises a gate electrode, gate insulating layer, an active layer, a source electrode and a drain electrode. A TFT also comprises a resistance layer between the active layer and the source electrode and/or between the active layer and the drain electrode to attain electric connection.

When a color display with a high precision is produced, TFT's are preferably formed on a color filter to precisely align them. Normal TFT with a low electric efficiency can not be down-sized much while obtaining the necessary driving current, and when a high precision display is pursued, the rate of the area for the TFT in a pixel must be high. When the rate of the area for the TFT is high, the rate of the opening area and contrast are low. Even when a transparent amorphous IGZO-type TFT is used, light transmittance is not 100% and reduction of contrast is unavoidable. Use of the TFT disclosed in JP-A 2009-21554 and the like can reduce the rate of the TFT in a pixel and improve the rate of the opening area and contrast. High precision can also be attained by forming this type of TFT on a color filter directly. (Others)

Other applications of the invention are thin-film transistors as in JP-T H10-512104 , touch panels as in JP-A 5-127822, 2002-48913, circularly polarizing plates as in JP-A-2002-865554, organic EL devices as in JP-A-2007-30387.

EXAMPLES

The characteristics of the invention are described more concretely with reference to the following Examples. In the following Examples, the material used, its amount and the ratio, the details of the treatment and the treatment process may be suitably modified or changed not overstepping the gist and the scope of the invention. Accordingly, the invention should not be limitatively interpreted by the Examples mentioned below. Formation of Gas Barrier Film (1)

PET film (COSMOSHINE A4300, having thickness of lOOpm) was cut into 10 cm square. On the surface thereof, an organic layer and an inorganic layer were formed by the following process. (Formation of Organic Layer)

On the PET film, a polymerizable composition consisting of polymerizable compounds having a composition shown the table below, 0.6 g of an ultraviolet polymerization initiator (manufactured by Chiba Specialty. Chemicals Inc. , Irgacure 184) , and 190 g of propylene glycol monomethyl ether acetate was coated using a wire bar, and was cured through irradiation with UV rays from a high-pressure mercury lamp (the total dose is 1.5 J/cm²) under oxygen concentration of 0.1 % or less by nitrogen substitution, thereby producing the organic layer having a thickness of about 1 pm. In the case of coating Compound F or Compound I, the polymerizable composition without an ultraviolet polymerization initiator was coated, and then dried at 80°C for 5 minutes .

(Formation of Inorganic Layer)

Using a deposition device capable of carrying out plasma-assisted deposition method based on EB+ ion gas system (manufactured by SHINCRON, ACE1350IAD) , an inorganic layer was formed on the organic layer by using SiO as a deposited source while carrying out oxygen plasma assist under the condition that the ion-assisted voltage was 900 V, the oxygen gas flow was 50 seem, and the argon gas flow was 8 seem. The thickness of the inorganic layer was 50 nm. The film formation speed was 5 nm/sec. It was found that the method of the invention achieved explicitly high film formation speed, taking into consideration that the film formation speed which was carried out by the sputtering method was 0.1 nm/sec.

(Measurement of Water Vapor Permeability by MOCON)

The waver vapor permeability of the obtained gas barrier film was evaluated using PERMATRAN-W3/31 manufactured by MOCON at 40°C for Relative Humidity (RH) of 90%. The results are shown below.

Formation of Gas Barrier Film (2) (Comparative Example)

As a comparative example, the gas barrier film was formed by the same method as the above formation of the gas barrier film (1) , except that compounds used for the formation of the organic layer were changed to the following compounds and that the ion assist voltage for forming the inorganic layer was optionally changed to 0 V according to the following table. The water permeability was evaluated according to the same method. The results are shown below.

[Table 1]

In the above table, the column of the organic layer shows the material for use in forming the organic layer. In the column of the inorganic layer, O shows that the inorganic layer was formed by the plasma-assisted deposition method and X shows that the inorganic layer was not formed by the plasma-assisted deposition method (that is, the ion assist voltage for forming the inorganic layer was 0 V) .

The above compounds in Table 1 are shown below.

Compound A: NK Oligo EA-1020, manufactured by Shin-Nakamura Chemical Co., Ltd.

Compound B: NK ester A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd.

Compound C: Mixture of NK Oligo EA-6320 , manufactured by Shin-Nakamura Chemical Co., Ltd., and TPGDA, manufactured by DAICEL-CYTEC COMPANY LTD.

Compound D: IRR214-K, manufactured by DAICEL-CYTEC COMPANY LTD. Compound F: Polystyrene average, weight-average molecular weight of 200000, manufactured by Aldrich

Compound G: Light acrylate BEPG-A, manufactured by Kyoeisha Chemical Co., Ltd.

Compound H: Methyl acrylate, manufactured by Aldrich

PMM (Polymethyl methacrylate) : weight-average molecular weight of 120000 (measured by GPC under powder state) , manufactured by Aldrich

Formation of Gas Barrier Film (3)

A gas barrier film was formed by the same method as in the above formation of gas barrier film (1) , except that SiO was replaced with A1₂0₃. It was found that the gas barrier films as obtained showed a similar tendency to the above gas barrier films.

Formation of Gas Barrier Film (4)

A multi-layered gas barrier film was formed by further forming an organic layer and an inorganic layer according to the same method as in the formation of gas barrier film (1) on the barrier laminate of the gas barrier film in the formation of gas barrier film (1) . The barrier property of the obtained gas barrier film was evaluated according to the above method. The results are shown below.

[Table 2]

Formation of Gas Barrier Film (5)

A gas barrier film was formed according to the same method as that in the above formation of gas barrier film (1), except that the inorganic layer was formed under the condition that the ion-assisted voltage was 450 V, the oxygen gas flow was 50 seem, and the argon gas flow was 8 seem. The water vapor permeability of the obtained gas barrier film was evaluated according to the above method. The results are shown below.

[Table 3]

Formation of Gas Barrier Film (6)

Two of the gas barrier films formed in the above formation of gas barrier film (1) were stuck to each other so that the barrier laminates face to each other using an adhesive (manufactured by Dainichi-Seika Color & Chemicals; main agent : E-372 , curing agent:C-76). The water vapor permeability of the obtained composite film was evaluated according to the above method. The results are shown below.

[Table 4]

Formation of Solar Cell

Using the gas barrier films as formed in the above gas barrier film (6), each of solar cell modules was manufactured. As filler for a solar cell module, standard cure type of ethylene-vinyl acetate copolymer was used. On the surface of a strengthen glass having a 10 cm square , amorphous series silicone cell for a solar cell was sandwiched to fill up ethylene-vinyl acetate copolymer films having a thickness of 450 μπι, and then, on the surface thereof, the above gas barrier film was provided to form a solar cell module. The solar cell module was set up by vacuuming it at 150°C for 3 minutes and pressuring it for 9 minutes . The solar cell module as formed according to the method of the invention worked properly and kept good electric generating power property even if used at 85°C and 85% RH.

The present disclosure relates to the subject matter contained in Japanese Patent Application No. 201313/2009 filed on September 1, 2009, which is expressly incorporated herein by reference in their entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.

The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.

Claims

1. A barrier laminate comprising at least one organic layer and at least one inorganic layer, wherein the organic layer comprises a resin having a cyclic skeleton consisting of carbon atoms, and the inorganic layer is formed by plasma-assisted deposition method.

2. The barrier laminate according to Claim 1, wherein the resin in the organic layer is an ultraviolet curable resin.

3. The barrier laminate according to Claim 1 or 2, wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a (meth) acrylate having a cyclic skeleton consisting of carbon atoms.

4. The barrier laminate according to any one of Claims 1 to 3, wherein the inorganic layer comprises silicon and/or aluminium.

5. The barrier laminate according to any one of Claims 1 to 4, wherein the inorganic layer is formed by using gas selected from argon gas, oxygen gas and a mixture thereof.

6. The barrier laminate according to any one of Claims 1 to 5, which comprises at least two organic layers and at least two inorganic layers laminated alternately.

7. The barrier laminate according to any one of Claims 1 to 6, wherein the resin in the organic layer is obtained by curing a polymerizable composition comprising a (meth) acrylate having an aromatic ring.

8. The barrier laminate according to any one of Claims 1 to 6, wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a polyfunctional (meth) acrylate .

9. The barrier laminate according to any one of Claims 1 to 6, wherein the resin in the organic layer is a resin obtained by curing a polymerizable composition comprising a polyfunctional (meth) acrylate having an aromatic ring.

10. The barrier laminate according to any one of Claims 1 to 6, wherein the cyclic skeleton consisting of carbon atoms is selected from benzene 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, perylene skeleton, and benzopyrene skeleton.

11. The barrier laminate according to any one of Claims 1 to 5, wherein the resin in the organic layer is obtained by curing a polymerizable composition comprising at least one kind of the following compounds:

12. The barrier laminate according to any one of Claims 1 to 11, wherein the plasma-assisted deposition method is carried out at an ion current density of 30 to 300 μΑ/cm², and at an ion-assisted voltage of 100 to 5000V.

13. The barrier laminate according to any one of Claims 1 to 12, wherein the organic layer has a thickness of 50 to 2000 nm and the inorganic layer has a thickness of 5 to 500 ran.

14. A gas barrier film comprising a substrate and the barrier laminate of any one of Claims 1 to 13 on the substrate.

15. A composite film comprising two gas barrier films, wherein the gas barrier films each are the gas barrier film of Claim 14 and are stuck to each other on a side of the barrier laminate .

16. A member for a solar cell, comprising the gas barrier film of Claim 14, or the composite film of Claim 15.

17. A method for manufacturing a barrier laminate comprising an organic layer and an inorganic layer,

wherein the organic layer comprises a resin comprising having a cyclic skeleton consisting of carbon atoms; and

18. The method for manufacturing the barrier laminate according to Claim 17, which further comprises forming the organic layer by curing a polymerizable composition comprising a (meth) acrylate having an aromatic ring.

19. The method for manufacturing the barrier laminate according to Claim 17 or 18, wherein the plasma-assisted deposition method is carried out at an ion current density of 30 to 300 μΑ/cm², and at an ion-assisted voltage of 100 to 5000V.

20. The method for manufacturing the barrier laminate according to any one of Claims 17 to 19, wherein the inorganic layer is formed in a clean room at the degree of cleanness of at most class 10000.