JP6251122B2 - Barrier film, laminated barrier film, and production method thereof - Google Patents

Description

  The present invention relates to a barrier film, a laminated barrier film, and a production method thereof.

  In a flexible device that is lightweight and can be bent freely, a gas barrier film is used as a sealing member used on a light emitting surface and a light receiving surface of a light emitting element or a photoelectric conversion element.

  For example, Patent Document 1 below discloses a gas barrier film including a thermoplastic film and an inorganic film laminated on the thermoplastic film and formed of zinc tin oxide. The mass ratio of zinc in the zinc tin oxide is set to 5% to 70%.

  Patent Document 2 below discloses a laminated moisture-proof film in which a base material on which an inorganic film is formed and a plastic film are laminated via a urethane-based adhesive. In Patent Document 2, the urethane adhesive can be applied by gravure coating.

JP 2010-524732 A JP 2012-148560 A

  However, the inorganic film made of zinc tin oxide disclosed in Patent Document 1 has a high refractive index. Therefore, when the inorganic film is provided on a resin material such as a thermoplastic film or an anchor coat layer, optical interference may occur due to a difference in refractive index between the resin material and the inorganic film. That is, the light transmittance of the barrier film tended to decrease.

  Further, as in Patent Document 2, when a laminated film is obtained by gravure-coating urethane adhesive on the inorganic film surface of the barrier film, the peel strength between the films is low, which may cause peeling. It was. That is, the gas barrier performance of the laminated film may be reduced.

  An object of the present invention is to provide a barrier film, a laminated barrier film, and a production method thereof having high transparency and excellent gas barrier performance.

  The barrier film according to the present invention includes a base material and an inorganic film laminated on the base material, and the inorganic film is formed of a complex oxide of Si, Zn, and Sn.

  The laminated barrier film according to the present invention is laminated on the surface of the adhesive layer opposite to the surface on which the barrier film is laminated, and the adhesive layer laminated on the barrier film. The film is provided.

  In the laminated barrier film according to the present invention, preferably, the adhesive layer is formed of a polyurethane adhesive or an acrylic adhesive.

  In the laminated barrier film according to the present invention, preferably, the film laminated on the surface of the adhesive layer opposite to the surface on which the barrier film is laminated is laminated on the substrate and the substrate. It is a barrier film having an inorganic film.

  The method for producing a barrier film according to the present invention is a method for producing a barrier film, comprising a step of preparing a base material for forming an inorganic film, and a double oxidation of Si, Zn and Sn on the base material. Forming an inorganic film formed of a material.

  In the method for producing a barrier film according to the present invention, preferably, the step of forming an inorganic film on the substrate includes a target formed of an alloy of Zn and Sn, and a target formed of Si. And a step of forming an inorganic film on the substrate by sputtering.

  The method for producing a laminated barrier film according to the present invention comprises a step of obtaining a barrier film by the method for producing a barrier film, a film that is the same as or different from the barrier film, and the film is bonded to the barrier film via an adhesive And a step of obtaining a laminated barrier film by bonding.

  In the barrier film and the laminated barrier film according to the present invention, an inorganic film formed of a double oxide of Si, Zn, and Sn is provided on a base material. Therefore, according to the present invention, a barrier film and a laminated barrier film having high transparency and excellent gas barrier performance can be provided.

It is a schematic block diagram of an example of the sputtering device used in order to produce the barrier film and laminated | multilayer barrier film which concern on this invention. It is sectional drawing of the lamination | stacking barrier film which concerns on the 1st Embodiment of this invention. It is sectional drawing of the lamination | stacking barrier film which concerns on the 2nd Embodiment of this invention.

  Details of the present invention will be described below.

  The barrier film according to the present invention includes a base material and an inorganic film. The inorganic film is laminated on the base material. The inorganic film is formed of a double oxide of Si, Zn, and Sn. Therefore, the barrier film according to the present invention is excellent in gas barrier performance.

  In addition, since the Si, Zn, and Sn double oxides have a relatively low refractive index, the difference in refractive index at the interface with the substrate is small. That is, since interference at the interface between the substrate and the inorganic film is suppressed, sufficient light transmittance is ensured. Therefore, the barrier film according to the present invention is also excellent in transparency.

  The laminated barrier film according to the present invention includes the barrier film, an adhesive layer, and a film that is the same as or different from the barrier film. On the inorganic film surface of the barrier film, a film that is the same as or different from the adhesive layer and the barrier film is laminated in this order.

  As described above, in the present invention, the inorganic film formed of the double oxide of Si, Zn, and Sn is in contact with the adhesive layer. Since the inorganic film formed of the Si, Zn, and Sn double oxide has high flexibility, it can contribute to the durability of the adhesive layer. That is, the stress generated at the interface with the adhesive layer can be dispersed by the flexibility of the inorganic film. Therefore, in this invention, generation | occurrence | production of peeling between films can be suppressed effectively. That is, according to the present invention, a laminated barrier film having excellent durability and gas barrier properties can be provided.

  Hereinafter, each layer of the barrier film and laminated barrier film of the present invention will be described in more detail.

(Base material)
Although it does not specifically limit as a base material, The resin film which has translucency is preferable. The resin constituting the resin film is not particularly limited, but acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and polybutyl acrylate, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, isophthalate copolymer At least one selected from polyester resins such as coalescence, polyolefin resins such as polyethylene resins and polypropylene resins can be used.

  From the viewpoint of transparency and adhesiveness to an inorganic film, the resin is preferably polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). The refractive index of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is about 1.6 to 1.75.

  The said base material may contain the other additive. Examples of such additives include an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a weathering stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, and an antioxidant.

  The resin film as the substrate may be stretched or unstretched. Further, the substrate may be a laminate of two or more resin films.

  Although the thickness of the said base material is not specifically limited, Usually, it is about 5 micrometers-200 micrometers. In order to improve productivity and handleability, 10 μm to 180 μm are preferable, and 35 μm to 90 μm are more preferable.

  In addition, an organic film may be provided between the base material and the inorganic film as long as the effects of the present invention are not impaired. When such an organic film is provided, the surface of the substrate can be further smoothed, and the adhesion with the inorganic film can be further enhanced.

  Examples of the organic film include an ethylene-unsaturated carboxylic acid-acrylic acid ester copolymer, an ethylene-unsaturated carboxylic acid-methacrylic acid ester copolymer, a thermoplastic elastomer, a low density polyethylene, and an ethylene-vinyl acetate copolymer. Polyether vinylidene chloride, ionomer, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, nitrocellulose, cellulose acetate, silicone, polyether polyurethane or diisocyanate and polyester which is a condensate of diisocyanate and polyether polyol Examples thereof include polyurethane resins such as polyester polyurethane which is a condensate of polyol.

  The thickness of the organic film is preferably 0.1 μm to 10 μm in order to enhance adhesion with the inorganic film and improve smoothness.

(Inorganic film)
In the present invention, an inorganic film is used by being laminated on the substrate in order to develop a gas barrier function. The inorganic film is formed of a double oxide of Si, Zn, and Sn. The inorganic film may be provided only on one side of the substrate, or may be provided on both sides of the substrate.

  Although content of Si in a double oxide is not specifically limited, It is preferable that it is 20 to 80 weight%, and it is more preferable that it is 30 to 70 weight%. When the content of Si is within the above range, a barrier film or a laminated barrier film having higher transparency and excellent gas barrier performance can be provided.

  The weight ratio of Zn to the total amount of Zn and Sn (Zn / Zn + Sn) in the double oxide is preferably 0.3 to 0.99, more preferably 0.5 to 0.9. preferable. When it exists in the said range, gas barrier property can be improved further.

  The thickness of the inorganic film is not particularly limited, but is preferably 30 nm to 3000 nm, and more preferably 50 nm to 1000 nm. When the film thickness is in the above range, the gas barrier performance can be further enhanced.

  The refractive index of the inorganic film is not particularly limited, but is preferably 1.9 or less, and more preferably 1.8 or less. Since the refractive index of polyethylene naphthalate or polyethylene terephthalate used as the base material is about 1.6 to 1.75, the base material and the inorganic film can be obtained by setting the refractive index of the inorganic film to 1.9 or less. The reflection of light at the interface can be further suppressed. That is, the transparency of the barrier film or the laminated barrier film is further enhanced.

(Adhesive layer)
The adhesive that forms the adhesive layer is not particularly limited as long as it is a transparent adhesive. Examples of the adhesive having transparency include urethane adhesives, acrylic adhesives, epoxy adhesives, one-part moisture-curing modified silicone adhesives, reactive adhesives such as cyanoacrylate adhesives, and chloroprene. Adhesives, solvent-based adhesives such as PVC adhesives, acrylic ester resins, styrene / acrylic ester resins, vinyl acetate resins, ethylene / vinyl acetate resins, ethylene / vinyl acetate / acrylic ester multi-component copolymers, etc. Emulsion adhesives such as these, or hot-melt adhesives based on polyamide, polyester, polyurethane, EVA, and acrylic resins can be used. Among these, polyurethane adhesives or acrylic adhesives are preferable because they have good productivity such as coating and are excellent in durability. Among these, a reactive polyurethane adhesive is particularly preferable.

  In the present invention, the adhesive preferably contains an ultraviolet absorber in order to improve weather resistance. Examples of ultraviolet absorbers that can be used include various types such as benzophenone-based, benzotriazole-based, triazine-based, salicylic acid ester-based, and various commercially available products can be applied. An ultraviolet absorber can also be used by 1 type and can also be used in combination of 2 or more type.

  The addition amount of the ultraviolet absorber is usually about 0.01 to 2% by mass and preferably 0.1 to 1% by mass in the adhesive.

  Further, in addition to the ultraviolet absorber, a hindered amine light stabilizer may be added in order to improve the weather resistance. A hindered amine light stabilizer does not absorb ultraviolet rays like an ultraviolet absorber, but exhibits a remarkable synergistic effect when used together with an ultraviolet absorber. The amount of the hindered amine light stabilizer added is usually about 0.01 to 1% by mass and preferably 0.1 to 0.5% by mass in the adhesive.

  In addition, when adding the said ultraviolet absorber and a hindered amine light stabilizer, what is necessary is just to add at least one of these.

(the film)
In the laminated barrier film according to the present invention, a film that is the same as or different from the barrier film is further laminated on the surface of the adhesive layer opposite to the side in contact with the inorganic film surface of the barrier film.

  In the case of a film different from the barrier film, for example, a film made of a fluororesin having excellent weather resistance is used for the purpose of protecting the inorganic film. However, the above-described polyethylene terephthalate (PET), polyethylene naphthalate (PEN), ethylene-tetrafluoroethylene copolymer (ETFE), or the like may be used.

  When it is the same film as the said barrier film, since the gas barrier performance of a lamination | stacking barrier film can be improved further, it is preferable. A plurality of films that are the same as or different from the barrier film may be laminated.

(Production method)
Barrier film manufacturing method:
The barrier film according to the present invention can be produced by forming an inorganic film on a base material or an organic film of a base material on which the organic film is formed. A method for forming the inorganic film is not particularly limited, but a vacuum film forming method is preferable because a uniform inorganic film can be obtained with improved barrier properties. Examples of the vacuum film formation method include physical vapor deposition methods (PVD) such as sputtering, vapor deposition, and ion plating, and chemical vapor deposition (CVD) such as plasma CVD using plasma. .

  FIG. 1 is a schematic configuration diagram as an example of a sputtering apparatus used for producing a barrier film and a laminated barrier film according to the present invention. The sputtering apparatus 1 has a film formation chamber 2. In the film forming chamber 2, a substrate holder 4 that can support the base material 3, a first cathode 5, and a second cathode 6 are provided. A target as a material can be attached to the first and second cathodes 5 and 6. For example, an alloy of Zn and Sn can be attached to the first cathode 5 and Si can be attached to the second cathode 6.

  The first and second cathodes 5 and 6 are connected to the first and second pulse power sources 7 and 8, respectively. Thereby, pulse power can be supplied to the first and second cathodes 5 and 6.

  Further, a vacuum pump 11, an argon gas supply line 9 and an oxygen gas supply line 10 are connected to the film forming chamber 2. Thereby, the inside of the film formation chamber 2 can be depressurized, and argon gas and oxygen gas can be supplied into the film formation chamber 2. As described above, after reducing the pressure in the film formation chamber 2 and supplying argon gas and oxygen gas at a predetermined flow rate, power is supplied to the first and second cathodes 5 and 6, so that the surface of the substrate 3 is applied. An inorganic film can be formed.

Manufacturing method of laminated barrier film:
The method for producing a laminated barrier film according to the present invention includes a step of obtaining a barrier film by the method for producing a barrier film, a film that is the same as or different from the barrier film, and the film is bonded to the barrier film via an adhesive. And a step of obtaining a laminated barrier film by bonding. In addition, the said adhesive agent is apply | coated to the inorganic film surface of the said barrier film, or the surface of a base material.

The adhesive can be applied by various coating methods. Examples of such a coating method include a roll coating method, a gravure roll coating method, and a kiss coating method. Especially, it is preferable to carry out gravure coating by a gravure roll coating method capable of ensuring a stable coating thickness even at a high coating speed. The coating amount is preferably in the range of 0.1 to 150 g / m ^{2 based on} the dry weight. Moreover, 1-50 micrometers is preferable and, as for the thickness of an adhesive bond layer, 3-30 micrometers is more preferable.

(Laminated form)
The laminated barrier film according to the present invention can take various laminated forms as long as the inorganic film and the adhesive layer are in contact with each other. Hereinafter, the lamination | stacking form which concerns on 1st, 2nd embodiment of the lamination | stacking barrier film of this invention is demonstrated, referring drawings. The present invention is not limited to these laminated forms.

  FIG. 2 is a cross-sectional view of the laminated barrier film according to the first embodiment of the present invention. The laminated barrier film 21 according to the first embodiment includes a barrier film 26, an adhesive layer 25, and a film 27.

  The barrier film 26 includes a base material 22, an organic film 23, and an inorganic film 24. On the base material 22, an organic film 23 and an inorganic film 24 are laminated in this order. The inorganic film 24 is formed of a double oxide of Si, Zn, and Sn. In the present embodiment, the organic film 23 is provided on the base material 22, but the organic film 23 is not provided. Also good.

  An adhesive layer 25 is provided on the inorganic film 24 of the barrier film 26. A film 27 is laminated on the surface of the adhesive layer 25 opposite to the surface in contact with the barrier film 26.

  FIG. 3 is a cross-sectional view of a laminated barrier film according to the second embodiment of the present invention. The laminated barrier film 31 according to the second embodiment includes two barrier films, that is, first and second barrier films 26A and 26B, and an adhesive layer 25.

  The first and second barrier films 26 </ b> A and 26 </ b> B include a base material 22, an organic film 23, and an inorganic film 24. On the base material 22, an organic film 23 and an inorganic film 24 are laminated in this order. However, the organic film 23 may not be provided in the first and second barrier films 26A and 26B.

  An adhesive layer 25 is laminated on the inorganic film 24 surface side of the first barrier film 26A. A second barrier film 26 </ b> B is laminated on the surface of the adhesive layer 25 opposite to the surface in contact with the inorganic film 24 so that the surface of the base material 22 is in contact with the adhesive layer 25. That is, the inorganic film 24 surface of the first barrier film 26 </ b> A and the base material 22 surface of the second barrier film 26 </ b> B are laminated so as to face each other with the adhesive layer 25 interposed therebetween. In this embodiment, two barrier films are laminated, but three or more barrier films may be laminated via the adhesive layer 25.

  In the laminated barrier film according to the present invention, as in the first and second embodiments, the inorganic film surface of at least one barrier film is laminated so as to be in contact with the adhesive layer, and the inorganic film Is formed of a double oxide of Si, Zn, and Sn. Therefore, the laminated barrier film according to the present invention is excellent in transparency, durability and gas barrier performance.

  Next, specific examples will be described. In addition, this invention is not limited to a following example.

Example 1
Substrate preparation:
A PEN film (manufactured by Teijin DuPont, product name “Q65FA”, thickness: 100 μm, refractive index = 1.75) was prepared as a base material for the barrier film.

Production of barrier film:
Next, an inorganic film was formed on the surface of the prepared PEN film in the film forming chamber 2 shown in FIG. Specifically, a PEN film was attached to the substrate holder 4, a ZnSn alloy (weight ratio Zn: Sn = 95: 5) target was attached to the first cathode 5, and a Si target was attached to the second cathode 6. Next, the film forming chamber 2 was evacuated by the vacuum pump 11 and decompressed to 5.0 × 10 ⁻⁴ Pa. Thereafter, sputtering was performed under the conditions shown in the following film formation condition A, a SiZnSnO film was formed as an inorganic film on the PEN film, and a barrier film was produced.

[Film formation condition A]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: 1st cathode = 500W, 2nd cathode = 1500W

(Example 2)
A barrier film was produced in the same manner as in Example 1 except that a ZnSn alloy (weight ratio Zn: Sn = 7: 3) target was attached to the first cathode 5.

(Comparative Example 1)
A ZnSn alloy (weight ratio Zn: Sn = 7: 3) is attached to the first cathode 5, and sputtering is performed under the conditions shown in the following film formation condition B, whereby ZnSnO is formed as an inorganic film on the PEN film used in Example 1. A film was formed to produce a barrier film.

[Film formation condition B]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: 1st cathode = 500W, 2nd cathode = 0W

(Comparative Example 2)
Al was attached to the second cathode 6, and sputtering was performed under the conditions shown in the following film formation condition C, and an AlO thin film was formed as an inorganic film on the PEN film used in Example 1 to produce a barrier film.

[Film formation condition C]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: 1st cathode = 0W, 2nd cathode = 1500W

(Evaluation)
About the obtained barrier film, the following evaluation items were evaluated.

(1) Water vapor transmission rate In order to evaluate the gas barrier property of the obtained barrier film, a JIS K 7126 A method (differential pressure method) was measured with a differential pressure type moisture permeability measuring device (product number “GTR-300XASC” manufactured by GTR Tech). The water vapor transmission rate was measured under the conditions of a temperature of 40 ° C. and a humidity of 90%.

(2) Total light transmittance About evaluation of the transparency of a gas barrier film, the total light transmittance was measured based on JISK7361 with the haze meter (the Toyo Seiki Seisakusho make, brand name "Haze guard 2").

(3) Refractive index The refractive index of the inorganic film was measured using a reflection spectral film thickness meter (trade name “FE-3000” manufactured by Otsuka Electronics Co., Ltd.).

  Details and results are shown in Table 1 below.

  Since the barrier films of Examples 1 and 2 are inorganic films made of a double oxide of Si, Zn and Sn, a barrier film having higher transparency than that of Comparative Example 1 could be obtained.

(Example 3)
Substrate preparation:
A PET film (manufactured by Teijin DuPont, product name “Q65FA”, thickness: 50 μm) was prepared as a base material for the barrier film.

Formation of organic film:
Next, an organic film was formed on the prepared PET film.

  Specifically, the composition for forming an organic film containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A), 63 parts by weight of tetraethoxysilane (B), and 4.9 parts by weight of water is added to 2- After adding 0.1 parts by weight of methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Ciba Specialty Chemicals, trade name “Irgacure 907”), 9 W Prepolymerization was performed by irradiating with ultraviolet rays for 15 minutes using an ultraviolet lamp.

  The prepolymerized composition was applied to one surface of the PET film prepared in advance, and the applied composition was subjected to an accelerating voltage of 175 kV using an electron beam irradiation apparatus (product name “EC300 / 165/800” manufactured by ESI). Radical polymerization of 3-methacryloxypropyltrimethoxysilane was performed by irradiating with an electron beam under an irradiation dose of 150 kGy to form a radical polymer.

  Next, the polyethylene terephthalate film having the composition irradiated with the electron beam on one side is left in an environment of 45 ° C. and a relative humidity of 65% RH for 1 hour, whereby 3-methacryloxypropyltrimethoxysilane in the radical polymer is obtained. The methoxy group derived from the ethoxy group of tetraethoxysilane is subjected to hydrolysis and dehydration condensation reaction, and the ethoxy group of tetraethoxysilane is subjected to hydrolysis and dehydration condensation reaction to crosslink between the main chains of the radical polymer. A dehydrated condensate of ethoxysilane was formed to obtain an organic film (thickness 5 μm).

Inorganic film:
An inorganic film was formed on the organic film in the same manner as in Example 1 to produce a barrier film. Two identical barrier films were produced.

Preparation of gravure coating solution:
A composition 100 in which a urethane resin (Mitsui Chemicals, trade name “Takelac A1102”) and a curing agent (Mitsui Chemicals, trade name “Takelac A3070”) are mixed so that the weight ratio is 16: 1. A gravure coating solution was prepared by adding 30 parts by weight of ethyl acetate to parts by weight.

Preparation of laminated barrier film:
The gravure coating solution was gravure-coated on the surface opposite to the inorganic film surface of the produced barrier film and dried to form an adhesive layer having a thickness of 10 μm. A laminate was prepared by bonding the urethane adhesive layer surface of the barrier film on which the urethane adhesive layer was formed and the inorganic film surface of the other barrier film prepared. On the inorganic film surface of the obtained laminate, an acrylic pressure-sensitive adhesive was applied with a thickness of 25 μm to form an adhesive layer, and an ETFE film with a thickness of 100 μm was bonded thereon to obtain a laminated barrier film.

Example 4
A gravure coating solution under the following conditions using an acrylic adhesive instead of a urethane resin when an inorganic film was formed in the same manner as in Example 2 instead of Example 1 and a laminated barrier film was produced. A laminated barrier film was produced in the same manner as in Example 3 except that an adhesive layer having a film thickness of 25 μm was formed instead of 10 μm.

Preparation of gravure coating solution:
A composition in which an acrylic adhesive (manufactured by Sekisui Chemical Co., Ltd., trade name “WHD”) and a curing agent (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”) are mixed so that the weight ratio is 100: 1.5. 100 parts by weight of the product, 5 parts by weight of toluene, 0.5 part by weight of a silane coupling agent (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.), an ultraviolet absorber (trade name “Adeka Stub LA36” manufactured by Adeka) A gravure coating solution was prepared by adding 0.4 parts by weight.

(Comparative Example 3)
In the same manner as in Example 3, an organic film was formed on the PET film. Next, Si is attached to the first cathode, and the SiOx thin film is formed as an inorganic film on the PET film by sputtering on the organic film under the conditions shown in the following film formation condition D, and two barrier films are formed. Produced.

  In this manner, a laminated barrier film was produced in the same manner as in Example 3 except that two barrier films were produced.

[Film formation condition D]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: 1st cathode = 2000W, 2nd cathode = 0W

(Comparative Example 4)
A laminated barrier film was produced in the same manner as in Example 3 except that the inorganic film was produced in the same manner as in Comparative Example 1 instead of Example 1.

(Evaluation)
The obtained laminated barrier film was evaluated for the following evaluation items.

(1) Total light transmittance About evaluation of the transparency of a lamination | stacking barrier film, the total light transmittance was measured based on JISK7361 with the haze meter (The Toyo Seiki Seisakusho make, brand name "Haze guard 2"). The total light transmittance was measured for a sample after 500 hours (after DH 500 hours) in an initial environment and a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH.

(2) Barrier film peel strength The peel strength between barrier films was measured using a universal material testing machine (trade name “Tensilon UTA-500” manufactured by Orientec Co., Ltd.) in accordance with JIS K6854-3. The T-type peel strength was measured at a test piece width of 15 mm and a peel rate of 200 mm / min. The T-type peel strength was measured for a sample after 500 hours (after DH 500 hours) in an initial environment and a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH.

(3) Water vapor transmission rate In order to evaluate the gas barrier property of the obtained laminated barrier film, the conditions of a temperature of 40 ° C. and a humidity of 90% were measured with a differential pressure type moisture permeability measuring device (product number “GTR-300XASC” manufactured by GTR Tech). Then, the water vapor transmission rate was measured.

  In addition, the water vapor transmission rate was measured for a sample after 500 hours (after DH 500 hours) in a high-temperature and high-humidity environment at an initial stage and a temperature of 85 ° C. and a humidity of 85% RH.

  Details and results are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 ... Sputtering apparatus 2 ... Film-forming chamber 3 ... Base material 4 ... Substrate holder 5 ... 1st cathode 6 ... 2nd cathode 7 ... 1st pulse power supply 8 ... 2nd pulse power supply 9 ... Argon gas supply line 10 ... Oxygen gas supply line 11 ... Vacuum pumps 21, 31 ... Laminated barrier film 22 ... Substrate 23 ... Organic film 24 ... Inorganic film 25 ... Adhesive layer 26 ... Barrier films 26A, 26B ... First and second barrier films 27 …the film

Claims (7)

A substrate;
An inorganic film laminated on the base material,
A barrier film in which the inorganic film is formed of a double oxide of Si, Zn, and Sn. A barrier film according to claim 1;
An adhesive layer laminated on the barrier film;
A laminated barrier film comprising: a film laminated on a surface opposite to a surface on which the barrier film of the adhesive layer is laminated.   The laminated barrier film according to claim 2, wherein the adhesive layer is formed of a polyurethane adhesive or an acrylic adhesive.   The film laminated | stacked on the surface on the opposite side to the surface where the barrier film of the said adhesive bond layer is laminated | stacked is a barrier film which has a base material and the inorganic film | membrane laminated | stacked on the said base material. The laminated barrier film according to 2 or 3. A method for producing a barrier film, comprising:
Preparing a base material for forming an inorganic film;
And a step of forming an inorganic film formed of a double oxide of Si, Zn, and Sn on the base material.   The step of forming an inorganic film on the base material uses a target formed of an alloy of Zn and Sn and a target formed of Si to form the inorganic film on the base material by a sputtering method. The manufacturing method of the barrier film of Claim 5 which is the process to form into a film. Obtaining a barrier film by the method for producing a barrier film according to claim 5 or 6,
Preparing a laminated barrier film by preparing a film that is the same as or different from the barrier film and bonding the film to the barrier film via an adhesive.

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