JP2013230605A - Gas barrier film and forming method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film that has proper gas barrier properties and suppresses more curl generation than a conventional gas barrier film even if a substrate film is thin, and to provide a method for forming the gas barrier film.SOLUTION: A lamination film including a silicon nitride film, a silicon oxide film and/or silicon oxynitride is formed on one surface side of a substrate film 5 of a thickness of 5-50 μm. A gas barrier film whose remaining stress of the entire lamination film is ±100 MPa, and a method for forming the gas barrier film are provided.

Description

  The present invention relates to a gas barrier film and a method for producing the same.

Conventionally, many films having an inorganic layer formed on a film using a plasma CVD method have been reported as gas barrier films.
For example, Patent Document 1 proposes a gas barrier film in which a silicon oxide film having a thickness of 100 nm is formed on a polyamide film having a thickness of 15 μm by using a plasma CVD method.

A film in which an inorganic layer is formed on a film using a catalytic chemical vapor deposition method instead of a plasma CVD method has also been reported.
For example, Patent Document 2 proposes a gas barrier film in which a silicon oxynitride film and a silicon nitride film are laminated in this order on a substrate. In the examples of this document, a gas barrier film excellent in water vapor barrier properties using a polyethersulfone substrate having a thickness of 100 μm is disclosed.

JP 2002-192646 A JP 2007-62305 A

However, the gas barrier film described in Patent Document 1 has a problem that the film is likely to curl due to residual stress in the inorganic layer. Further, since the plasma CVD method is used, the substrate may be damaged by the plasma.
In Patent Document 2, moisture penetration from the film end face may be a problem with the substrate thickness disclosed in the examples, and depending on the configuration of the solar cell, the touch panel, and the organic LED device, it is suitable as a gas barrier film. I can't say that.

Here, the substrate (base film) is further referred to. That is, in the roll-to-roll type gas barrier film manufacturing apparatus, the winding length for each roll varies depending on the thickness of the substrate. It needs to be thin.
Further, when the base film is thick, there is a problem that the manufacturing cost of the gas barrier film is increased accordingly.
Therefore, it is conceivable to use a base film having a smaller thickness. However, as disclosed in Examples of Patent Document 2, when an inorganic layer having a thickness of 100 nm or more is deposited on a thin base film, There was a problem that the film was likely to curl.

  In view of the above, an object of the present invention is to solve the above conventional problems. That is, an object of the present invention is to provide a gas barrier film that has good gas barrier properties and that suppresses the amount of curling compared to the conventional method even when the base film is thin, and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors laminated a gas barrier film that expresses tensile stress and a gas barrier film that expresses compressive stress on one surface side of a base film having a predetermined thickness. Then, by controlling the residual stress of the laminated film formed thereby to a predetermined range, it has been found that a gas barrier film having a good gas barrier property and a curl generation amount suppressed compared to the conventional one can be obtained, The present invention has been conceived. That is, the present invention is as follows.

[1] A laminated film including a silicon nitride film and a silicon oxide film and / or a silicon oxynitride film is formed on one surface side of a base film having a thickness of 5 to 50 μm. A gas barrier film having a residual stress of ± 100 MPa.
[2] The film thickness ratio (A / B) between the film thickness A of the silicon nitride film and the film thickness B of the silicon oxide film and / or the silicon oxynitride film is 1 to 4. Gas barrier film.
[3] The thicknesses of the silicon oxide film, the silicon oxynitride film, and the silicon nitride film are each independently 20 to 500 nm, the thickness X of the base film, and the thickness Y of the laminated film The gas barrier film according to [1] or [2], wherein the ratio (Y / X) satisfies the condition represented by 0.002 to 0.08.
[4] The gas barrier film according to any one of [1] to [3], wherein the warpage amount of the film is 3 mm or less in the evaluation of the warpage of the film.
[5] A laminated film including the silicon nitride film and a silicon oxide film and / or a silicon oxynitride film is formed by catalytic chemical vapor deposition using silane gas as a source gas. 4] The gas barrier film according to any one of the above.
[6] A laminated film including a silicon nitride film, a silicon oxide film and / or a silicon oxynitride film is formed on one surface side of a base film having a thickness of 5 to 50 μm by catalytic chemical vapor deposition. A method for producing a gas barrier film, comprising a laminated film forming step in which the residual stress of the whole laminated film is within a range of ± 100 MPa.

  ADVANTAGE OF THE INVENTION According to this invention, even if the gas barrier property is favorable and the base film is thin, the gas barrier property film with which the generation amount of curl was suppressed compared with the past and its manufacturing method can be provided.

It is explanatory drawing which shows roughly an example of the apparatus for implementing a catalytic chemical vapor deposition method. It is explanatory drawing which shows the method of the curvature evaluation of a film roughly.

[1. Gas barrier film]
The gas barrier film of the present invention is formed by forming a laminated film including a silicon nitride film, a silicon oxide film and / or a silicon oxynitride film on one surface side of a base film having a thickness of 5 to 50 μm.
By laminating the silicon nitride film and the silicon oxide film and / or the silicon oxynitride film, excellent gas barrier properties that cannot be achieved independently can be exhibited.
In consideration of gas barrier properties, it is preferable that a silicon oxide film or a silicon oxynitride film is formed as the first layer on the film base. Moreover, it is preferable that the thickness of a base film is 10-40 micrometers.

The laminated film of the gas barrier film of the present invention has an overall residual stress in the range of ± 100 MPa. When the residual stress exceeds 100 MPa, the laminated film shrinks with respect to the base film due to the tensile stress, and the laminated film curls on the concave side. When the residual stress is less than −100 MPa, the curled film on the convex surface side is caused by the compressive stress. Further, by controlling the residual stress within such a range, even when the thickness of the base film is as thin as 5 to 50 μm, the gas barrier property is good and the amount of curling can be suppressed.
The residual stress is preferably -80 to 80 MPa, and more preferably -50 to 50 MPa. A method for measuring the residual stress will be described later.

In order to make the residual stress in the range of ± 100 MPa, it is necessary to laminate an inorganic film having a tensile stress and an inorganic film having a compressive stress on one surface side of the base film in a predetermined film thickness ratio.
As the inorganic film, an inorganic silicon film exhibiting gas barrier properties is preferable, and specific examples include a silicon nitride film, a silicon oxynitride film, a silicon oxide film, and a silicon carbide film.
A silicon nitride film formed by catalytic chemical vapor deposition using silane gas as a raw material exhibits tensile stress, and a silicon oxynitride film and a silicon oxide film exhibit compressive stress, but these inorganic silicon films are formed at a predetermined film thickness ratio. By laminating, the residual stress can be in the range of ± 100 MPa.

The film thickness ratio (A / B) between the film thickness A of the silicon nitride film and the film thickness B of the silicon oxide film and / or the silicon oxynitride film is preferably 1 to 4, more preferably 1.5 to 3. It is more preferable.
When the film thickness ratio is 1 to 4, the gas barrier film is not extremely curled, and excellent gas barrier properties can be maintained.

The thicknesses of the silicon oxide film, the silicon oxynitride film, and the silicon nitride film are each independently 20 to 500 nm, and the ratio (Y / X) between the thickness X of the base film and the thickness Y of the laminated film is , 0.002 to 0.08 are preferably satisfied.
If it is in the said range, since the whole laminated film is sufficiently thick, it exhibits excellent gas barrier properties, and the adhesion between the base film and each film also becomes good.

  The thicknesses of the silicon oxide film, the silicon oxynitride film, and the silicon nitride film are more preferably independently from 50 to 300 nm. The ratio between the thickness X of the base film and the thickness Y of the laminated film is more preferably 0.002 to 0.05, and further preferably 0.005 to 0.05.

The base film of the gas barrier laminate film of the present invention is preferably a plastic film from the viewpoint of processability. The raw material thereof can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials.
Specifically, homopolymers such as ethylene, propylene, and butene, or polyolefins that are copolymers thereof; amorphous polyolefins such as cyclic polyolefins; polyesters such as polyethylene terephthalate and polyethylene naphthalate: nylon 6, nylon 66, Polyamide such as nylon 12 and copolymer nylon; ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, polyvinyl butyral, polyarylate , Polymethacrylic resin, fluorine resin, acrylic resin, biodegradable resin, and the like. Among these, polyester, polycarbonate, polymethacrylic resin, polyethersulfone, and cyclic polyolefin are preferable from the viewpoint of film strength, cost, and the like, and polyester is more preferable.
In particular, in the case of an EL substrate or a liquid crystal display element, the base film is preferably a heat resistant resin such as polyethylene naphthalate, polyether imide, or polyether sulfone from the viewpoint of heat resistance.
The base film is a known additive such as an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, and an antioxidant. An agent etc. can be contained.

  Further, the surface roughness (Rms) of the base film is preferably 1.5 nm or less. When Rms is 1.5 nm or less, the thin film is formed to have a uniform thickness, and the particles forming the thin film are easily densely packed, so that a high oxygen gas barrier property and water vapor barrier property can be obtained. As a result, the thickness of the laminated film can be reduced.

  The plastic film as the base film is formed by molding the above raw material, but when used as the base film, it may be unstretched or stretched. Moreover, either a single layer or a multilayer may be sufficient. Such a substrate film can also be produced by a conventionally known method. For example, the raw material is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be oriented in an amorphous manner. No unstretched film can be produced. This unstretched film is subjected to a known stretching method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A film stretched in a uniaxial direction or a biaxial direction can be produced by stretching in the flow direction and a direction perpendicular to the flow direction (horizontal axis direction). In the present invention, the base film is preferably biaxially stretched from the viewpoint of mechanical strength.

From the above viewpoint, the draw ratio is preferably 2 to 6 times, more preferably 2 to 4 times, and preferably 2 to 5 times, more preferably 2 to 4 times in the horizontal axis direction. Moreover, it is preferable that the said base film is 0.01 to 5% of the thermal contraction rate after the hot-water process at 120 degreeC.
There is no restriction | limiting in particular about the width | variety and length of a base film, According to a use, it can select suitably.

In the present invention, it is preferable to provide an anchor coat layer by applying an anchor coating agent between the base film and the laminated film in order to improve the adhesion with the laminated film.
Examples of the anchor coating agent include polyester resins, urethane resins, acrylic resins, nitrocellulose resins, silicone resins, polyvinyl alcohol resins such as vinyl alcohol resins and ethylene vinyl alcohol resins, vinyl ester resins, and oxazolines. A group-containing resin, a carbodiimide group-containing resin, an epoxy group-containing resin, an isocyanate group-containing resin, an alkoxyl group-containing resin, a styrene resin, or the like can be used alone or in combination of two or more.
Among them, polyester resin, urethane resin, acrylic resin, nitrocellulose resin, silicone resin, vinyl alcohol resin, oxazoline group-containing resin, carbodiimide group-containing resin and isocyanate group from the viewpoint of adhesion and hot water resistance It is preferable to use at least one selected from the containing resins, and further, one or more of urethane-based resins and acrylic resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, and isocyanate group-containing resins. What combined 1 or more types is preferable.

The thickness of the anchor coat layer is preferably about 0.005 to 5 μm, and more preferably 0.01 to 1 μm. If it is in the said range, slipperiness is favorable, there is almost no peeling from the base film by the internal stress of anchor coat layer itself, and uniform thickness can be maintained.
Moreover, in order to improve the applicability | paintability of an anchor coating agent to a base film, and adhesiveness, you may perform surface treatments, such as a normal chemical treatment and electrical discharge treatment, before application | coating of an anchor coating agent.

The gas barrier film of the present invention can be made into a gas barrier film corresponding to various uses by further laminating other layers.
As a lamination method, a dry lamination method using an adhesive or an extrusion lamination method using an adhesive resin can be used.
As a normal embodiment, a laminate in which a plastic film is provided on the laminated film surface and / or the base film surface according to the present invention is used for various applications. The thickness of the plastic film is usually 5 to 500 μm from the viewpoint of overall mechanical strength, flexibility, transparency, and the like, and is preferably selected depending on the application within the range of 10 to 200 μm. Further, the width and length of the film are not particularly limited and can be appropriately selected according to the intended use. For example, by laminating a heat-seal layer of a plastic film made of a heat-sealable resin on the laminated film surface and / or the base film surface, heat sealing becomes possible and it can be used as various containers. Examples of heat sealable resins include known resins such as polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, acrylic resins, and biodegradable resins.

As an embodiment of the gas barrier film other than the above, there is a film in which a printed layer is formed on the laminated film surface, and a heat seal layer or a plastic film is further laminated thereon. As the printing ink for forming the printing layer, aqueous and solvent-based resin-containing printing inks can be used.
Here, examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Furthermore, for printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These known additives may be added.

  Further, at least one layer of paper or other plastic film can be laminated between the printing layer and the heat seal layer or the plastic film. As said plastic film, the thing similar to the plastic film as a base film used for the gas barrier film of this invention can be used. Among these, from the viewpoint of obtaining sufficient rigidity and strength, a polyester resin, a polyamide resin, or a biodegradable resin is preferable.

In the gas barrier film of the present invention as described above, the amount of warpage of the film is preferably 3 mm or less and more preferably 1 mm or less in the evaluation of the warpage of the film.
Moreover, it is preferable that barrier property, especially water vapor | steam barrier property are 0.4 g / m < ² > / day or less. In addition, the curvature of a film and evaluation of water vapor | steam barrier property are mentioned later.

[2. Method for producing gas barrier film]
In the method for producing a gas barrier film of the present invention, a laminated film including a silicon nitride film, a silicon oxide film and / or a silicon oxynitride film is formed on one surface side of a base film having a thickness of 5 to 50 μm by catalytic chemistry. It includes a step of forming a laminated film that is formed by vapor phase epitaxy to bring the residual stress of the whole laminated film into a range of ± 100 MPa.

In the laminated film forming step according to the present invention, the barrier property can be improved by applying the catalytic chemical vapor deposition method to form the laminated film.
In this catalytic chemical vapor deposition method, a base film is obtained by heating a metal catalyst wire as a heating catalyst body under vacuum and bringing one or more material gases into contact with the metal catalyst wire and thermally decomposing them. A film having an element constituting the main source gas as a main skeleton material can be formed thereon.

  In the catalytic chemical vapor deposition method, the temperature of the base film is preferably cooled to a glass transition temperature (Tg) of the base film or lower, more preferably to Tg-10 ° C. or lower. Thereby, laminated film material can be deposited below the glass transition temperature of a base film, and the damage of the base film by the radiant heat from a metal catalyst body can be eliminated.

Further, the reaction pressure is preferably carried out under a reduced pressure of 100 Pa or less from the viewpoints of preventing impurities in the air from being mixed into the film and the film formation speed. Conventional catalysts such as tungsten, platinum, and nickel can be used as the metal catalyst body as the heating catalyst body. However, the metal catalyst body itself does not melt or volatilize at the temperature at which the material gas is catalytically decomposed, and further silicidation occurs. Tungsten is preferable because it is suppressed and corrosion by halogen is suppressed.
The shape of the line of the metal catalyst body may be a straight line, or may be a right cylindrical coil, may have other shapes, and may have a structure other than a line. The total area of the heating catalyst body is preferably 1000 to 5000 mm ² from the viewpoint of film formation speed, the amount of heat radiation from the heating catalyst body to the base film, the supply power of the heating catalyst body, etc., and 1500 to 3000 mm. ² is more preferable. The temperature of the metal catalyst body is a temperature at which the material gas is catalytically decomposed, and is preferably a temperature that does not cause thermal damage to the deposit, preferably 500 to 2500 ° C, more preferably 1600 to 2000 ° C. .

  The material gas that can be used varies depending on the target film composition, but is preferably composed of at least one kind of gas, and rare gases such as ammonia, nitrogen, oxygen, hydrogen, and argon are included in the first material gas containing silicon. It is preferable to use a gas as the second material gas.

Examples of the first material gas containing silicon include monosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane. Ethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, etc. alone or 2 It can be used in combination of more than one species.
The material gas may be gaseous or liquid at room temperature, and the liquid raw material can be vaporized by a raw material vaporizer and supplied into the apparatus. Among the first material gases, monosilane gas is preferable in terms of residual stress control, deterioration of the heating catalyst body, reactivity, and reaction rate.

The main reaction at and near the surface of the heated catalyst body when using monosilane gas is
SiH ₄ → Si · + 4H · and SiH ₄ + H · → SiH ₃ · + H ₂
SiH _3. Is considered to be the main deposition species.
The main reaction of ammonia is
NH ₃ → NH ₂ + H
NH _2. Is considered to be the main sedimentary species.
The main reaction of hydrogen is
H ₂ → 2H ・
H. is considered to be mainly used to assist the gas phase reaction and the surface reaction of the substrate film.

Although H. is generated without using hydrogen as a material gas, a large amount of H. can be generated by flowing hydrogen into a vacuum apparatus as a material gas. Demonstrating. And, it is presumed that SiH ₃ · and NH ₂ · mainly react with the presence of reaction auxiliary components such as thermal energy on the substrate film surface, thermal energy of the deposited species, H ·, etc., to become a silicon nitride film, Detailed gas phase reactions and substrate surface reactions are not known.
In addition, in the above, * shows the state of a radical.

  The material gas flow ratio is preferably 0 to 30, more preferably 0 to 10, ammonia is preferably 5 to 400, more preferably 20 to 80, and oxygen is preferably 0 to 2.0 with respect to monosilane 1. More preferably, it is 0-0.8. By forming the film within such a range, it is possible to form a silicon oxide film, a silicon oxynitride film, and a silicon nitride film that are highly transparent and have good adhesion properties that prevent permeation of water vapor, oxygen, and the like. .

Here, preferable ranges for the silicon oxynitride film composition are a nitrogen / silicon ratio (N / Si) of 0.1 to 0.3 and an oxygen / silicon ratio (O / Si) of 0.8 to 1.6. A preferred range for the silicon nitride film composition is a nitrogen / silicon ratio (N / Si) of 0.6 to 1.4. A preferred range for the silicon oxide film composition is an oxygen / silicon ratio (O / Si) of 1.2 to 2.0.
The deposition conditions are adjusted so that the composition and the desired thickness are obtained, and the residual stress of the entire laminated film is within a range of ± 100 MPa.
The gas barrier film of the present invention is produced through such a laminated film forming step.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples.

First, various measurements and evaluations performed in this example will be described.
(1) Measurement of film thickness Using a sample in which various films were formed on a Si wafer under the same conditions as in Examples 1 to 4 and Comparative Examples 1 to 3, a stylus step meter (manufactured by KLA-Tencor, product No. Alpha-Step 500).

(2) Residual stress measurement Before the formation of various films, the amount of warpage in the longitudinal direction of the strip-shaped glass substrate was measured using a stylus-type step gauge (manufactured by Kosaka Laboratory, product name Surfcoder ET4000A).
Then, after forming various films | membranes on the glass substrate on the same conditions as each of Examples 1-4 and Comparative Examples 1-3, the curvature amount of the longitudinal direction of the glass substrate was measured. From the measurement results, the radius of curvature of the glass substrate and the residual stress of the laminated film were calculated.
The following formula was used for calculating the residual stress of the laminated film.

: Residual stress of laminated film: Young's modulus of glass substrate: Poisson's ratio of glass substrate: Thickness of glass substrate: Thickness of laminated film: Curvature radius of curvature of glass substrate after film formation: Radiation of glass substrate before film formation Curvature radius of curvature

  In addition, the glass substrate used what was cut out in strip shape (3 mm x 24 mm) using the cover glass (square No. 1) by Matsunami Glass Industry.

(3) Element measurement by ESCA Using a X-ray photoelectron spectrometer (K-Alpha, manufactured by Thermo Fisher Scientific Co.), the binding energy of the gas barrier film is measured, and peaks corresponding to Si2p, C1s, and O1s The elemental composition (at.%) Of various films was calculated by converting from the area. The element ratios O / Si and N / Si were calculated from the elemental composition of Si and O and Si and N.

(4) Measurement of water vapor permeability of gas barrier laminate film (production of gas barrier laminate film)
Apply a urethane adhesive (containing Toyo Morton's AD900 and CAT-RT85 in a ratio of 10: 1.5) on the surface of a 60 μm thick CPP film (P1146, manufactured by Toyobo Co., Ltd.) and dry. Then, an adhesive layer having a thickness of about 3 μm was formed. On this adhesive layer, the laminated film surface side of the gas barrier film produced in Examples and Comparative Examples was laminated to obtain a gas barrier laminated film.

(Measurement of water vapor permeability)
The gas barrier laminated film is set in a water vapor transmission rate measuring device DELTAPERRM (Technolox) in such a direction that the gas barrier film is on the detector side (CPP film is on the water vapor exposure side), and the temperature is 40 ° C. and the relative humidity is 90%. The water vapor transmission rate (g / m ² / day) was measured.

(5) Warpage evaluation of the film As shown in FIG. 2, the gas barrier film 8 was cut into 50 mm × 50 mm, neutralized by a blow type static electricity removing unit, and then horizontally with the convex side of the gas barrier film 8 facing down. It was left on the table 7. The distance in the vertical direction between the four corners and the horizontal plane (measurement distance 9) was measured to calculate an average value, which was taken as the amount of warpage of the film (curl generation amount).
Note that FIG. 2 is exaggerated for easy understanding.

[Example 1]
(Formation of anchor coat layer)
An isocyanate compound (Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.) and saturated polyester (Toyobo Co., Ltd. Byron 300) were blended at a ratio of 1: 1 (mass ratio) to prepare a coating solution.
A polyethylene naphthalate film having a thickness of 12 μm (Cornate L, hereinafter abbreviated as “PEN film”) was used as a base film, and the coating solution prepared on this one side surface was applied and dried to form an anchor coat layer having a thickness of 10 nm. .

(Formation of laminated film)
A laminated film was formed using the catalytic chemical vapor deposition (Cat-CVD) apparatus shown in FIG. First, a PEN film as the base film 5 is fixed to the substrate holder 4, the distance between the PEN film and the heating catalyst body 2 is 200 mm, the temperature of the PEN film before vapor deposition is 60 ° C., and the material of the heating catalyst body 2 is φ0. The temperature of the heating catalyst body 2 was set to 1800 ° C. with tungsten of 5 × 1250 mm. Thereafter, oxygen (O ₂ ), silane (SiH ₄ ), ammonia (NH ₃ ), and hydrogen gas (H ₂ ) as raw material gases were supplied into the film forming chamber 1 from the gas inlet 3 installed on the upper part of the catalyst body. . The gas after the reaction was exhausted from the exhaust port 6.
In addition, the arrow in FIG. 1 shows the flow direction of gas.

Using the above apparatus, the film was deposited under a vacuum of 20 Pa (0.15 Torr) with a mixing ratio (volume ratio) of the source gases of SiH ₄ : H ₂ : NH ₃ = 1: 40: 2.2, and an anchor coat layer A SiNx film (silicon nitride film) having a thickness of about 159 nm was formed on the formation surface side.

Once exhausted to lower the degree of vacuum and the temperature of the catalyst body, the mixing ratio of the raw material gases was again changed to SiH ₄ : H ₂ : NH ₃ : O ₂ (He dilution) = 1: 40: 2.2. The film was formed under a vacuum of 20 Pa (0.15 Torr) at 0.6, and a SiOxNy film (silicon oxynitride film) having a thickness of about 80 nm was formed on the laminated film to produce a gas barrier film (total Film thickness 239 nm Film thickness ratio SiNx film: SiOxNy film = 2: 1).
Elemental measurement by ESCA was performed on the produced gas barrier film. The results are shown in Table 1 below.
Moreover, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

(Example 2)
In Example 1, the laminated film was formed on the PEN film in the same manner except that the total film thickness of the laminated film of the SiNx film and the SiOxNy film was changed to 307 nm (film thickness ratio SiNx film: SiOxNy film = 2: 1). Then, a gas barrier film was produced.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

(Example 3)
In Example 1, the laminated film was formed on the PEN film in the same manner except that the total film thickness of the laminated film of the SiNx film and the SiOxNy film was changed to 405 nm (film thickness ratio SiNx film: SiOxNy film = 2: 1). Then, a gas barrier film was produced.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

Example 4
In Example 1, a laminated film was similarly formed on the PEN film except that the total film thickness of the laminated film of the SiNx film and the SiOxNy film was changed to 501 nm (film thickness ratio SiNx film: SiOxNy film = 2: 1). did.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

(Comparative Example 1)
A gas barrier film was produced in the same manner as in Example 1 except that no SiNx film was formed and only a 385 nm thick SiOxNy film was formed on the PEN film.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.
In the evaluation of the warpage of the film, the film was curled and the four corners were rounded, so measurement was not possible.

(Comparative Example 2)
A gas barrier film was produced in the same manner as in Comparative Example 1 except that the thickness of the SiOxNy film was changed to 114 nm.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

(Comparative Example 3)
In the same manner as in Example 1, except that the thickness of the SiNx film was changed to 96 nm and the thickness of the SiOxNy film was changed to 191 nm (total film thickness ratio 287 nm, film thickness ratio SiNx film: SiOxNy film = 1: 2). A laminated film was formed thereon to produce a gas barrier film.
About the produced gas barrier film, the residual stress measurement and the curvature evaluation of the film were performed. Moreover, the water vapor permeability was measured for the gas barrier laminate film. The results are shown in Table 2 below.

1: Film formation chamber 2: Heated catalyst body 3: Gas introduction port 4: Substrate holder 5: Base film 6: Exhaust port 7: Horizontal base 8: Gas barrier film 9: Measurement distance

Claims (6)

  A laminated film including a silicon nitride film, a silicon oxide film and / or a silicon oxynitride film is formed on one surface side of the base film having a thickness of 5 to 50 μm, and the residual stress of the whole laminated film is Gas barrier film that is ± 100 MPa.   2. The gas barrier film according to claim 1, wherein a film thickness ratio (A / B) between the film thickness A of the silicon nitride film and the film thickness B of the silicon oxide film and / or the silicon oxynitride film is 1 to 4. . The silicon oxide film, the silicon oxynitride film, and the silicon nitride film each independently have a thickness of 20 to 500 nm,
The gas barrier property according to claim 1 or 2, wherein a ratio (Y / X) between a thickness X of the base film and a thickness Y of the laminated film satisfies a condition represented by 0.002 to 0.08. the film.   The gas barrier film according to any one of claims 1 to 3, wherein a warpage amount of the film is 3 mm or less in evaluation of warpage of the film. The laminated film including the silicon nitride film and the silicon oxide film and / or the silicon oxynitride film is formed by catalytic chemical vapor deposition using silane gas as a source gas. The gas barrier film according to Item.   A laminated film including a silicon nitride film and a silicon oxide film and / or a silicon oxynitride film is formed on one surface side of a base film having a thickness of 5 to 50 μm by a catalytic chemical vapor deposition method, A method for producing a gas barrier film, comprising a laminated film forming step in which the residual stress of the entire film is within a range of ± 100 MPa.