JP5300765B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film used for food packaging, liquid crystal display, plasma display, organic EL display, solar cell, and the like, and particularly relates to a gas barrier film having high gas barrier performance.

Used for packaging parts such as optical elements, display devices such as liquid crystal displays and organic EL displays, semiconductor devices, thin film solar cells, and other parts and parts that require moisture resistance, or food, clothing, electronic parts, etc. A gas barrier film is used, which is formed by forming a film (hereinafter also referred to as a gas barrier film) on a plastic film (substrate film) such as a polyethylene terephthalate (PET) film as a packaging material.
As a gas barrier film formed on such a gas barrier film, films made of various inorganic substances (inorganic compounds) such as silicon nitride, silicon oxide, and aluminum oxide are known. Among these gas barrier films, some silicon oxide films focus on the relationship between a specific wave number and gas barrier performance in infrared absorption spectra (for example, Patent Documents 1 and 2).

For example, Patent Literature 1 discloses a gas barrier film in which a thin film containing silicon oxide as a main component is formed on at least one surface of a base material. The gas barrier film of the infrared absorption spectrum of a thin ^film, the ratio p2 / p1 of the peak intensity p2 existing between the peak intensities p1 and ^{940cm -1 ~850cm} -1 existing between 1040cm ^-1 ~1080cm -1 However, 0 ≦ p2 / p1 ≦ 0.2 is satisfied.
Note that the maximum intensity peak existing at 1040 cm ^{−1 to} 1080 cm ⁻¹ is absorption due to asymmetric stretching motion of Si—O—Si, and the maximum intensity peak existing at 940 cm ^{−1 to} 850 cm ⁻¹ is Si—O—H. Absorption peak due to binding.

In Patent Document 1, when the ratio p2 / p1 is larger than 0.2, structural defects due to Si—O—H are large in the thin film, and sufficient gas barrier properties and moisture resistance cannot be obtained. The Si—O—H bond observed at 850 cm ⁻¹ is a cause of barrier performance deterioration. Patent Document 1 discloses a gas barrier film having a water vapor transmission rate of 0.2 g / (m ² · day).

Patent Document 2 discloses a transparent barrier film having at least a base film and a barrier layer provided on at least one surface of the base film. This transparent barrier film is a thin film mainly composed of silicon oxide having a four-membered ring structure of silicon atoms and oxygen atoms formed by a chemical vapor deposition method using a siloxane having a four-membered ring structure as a source gas. . The barrier layer has a peak area S1 of stretching vibration absorption (Si—O—Si stretching mode) composed of silicon atoms and oxygen atoms in the vicinity of 1240 cm ⁻¹ in a spectrum measured by infrared spectroscopy, and a peak by a curve fitting method. It was expressed as the sum of Gaussian and Lorentzian distribution, the peak position, height, half width, Gaussian and 4-membered ring by a silicon atom and an oxygen atom in the vicinity of 890 cm ^-1 obtained by analyzing the ratio of the Lorentz distribution as a parameter There is a relationship in which the ratio (S2 / S1) is 0.01 or more with the absorption peak area S2 of the structure.

In Patent Document 2, when the ratio (S2 / S1) is less than 0.01, a four-membered ring structure composed of silicon atoms and oxygen atoms existing in the barrier layer becomes insufficient, and high barrier properties cannot be obtained. It is said. It is said that a high barrier property is obtained by having a four-membered ring structure of SiO observed around 890 cm ⁻¹ . Patent Document 2 discloses a transparent barrier film having a water vapor transmission rate of 1.5 g / (m ² · day).

JP-A-8-224825 Japanese Patent No. 3820041

Patent Document 1 described above, is used ^{1040cm -1 ~1080cm} -1 is the absorption due to the asymmetric stretching vibration of Si-O-Si in the evaluation of the barrier properties. In Patent Document 2, the vicinity of 1240 cm ^−1, which is stretching vibration absorption (Si—O—Si stretching mode) composed of silicon atoms and oxygen atoms, is used for barrier property evaluation.
As described above, Patent Documents 1 and 2 both standardize the absorption band relating to the expansion and contraction of Si—O—Si in the infrared absorption spectrum and define the amount of each bond.

However, the absorption band related to Si—O—Si specified in Patent Documents 1 and 2 has a problem that the peak position is shifted depending on the composition of the SiOx film (where x represents the degree of oxidation). For this reason, in Patent Documents 1 and 2, the water vapor transmission rate is about 0.2 g / (m ² · day). At present, the absorption band relating to Si—O—Si used is insufficient.

  An object of the present invention is to solve the problems based on the above prior art, pay attention to the absorption spectrum of silicate in the infrared absorption spectrum, and define the absorption spectrum, thereby providing a gas barrier having excellent gas barrier performance. To provide a film.

In order to achieve the above object, an aspect of the present invention is a gas barrier film in which a gas barrier film containing silicon oxide as a main component is formed on at least one surface of a substrate, and the gas barrier film has an infrared absorption spectrum. Of these, when the peak intensity at 800 to 820 cm ⁻¹ is P1, the peak intensity at 860 to 880 cm ⁻¹ is P2, and the ratio of the peak intensity P1 and the peak intensity P2 is P2 / P1, the ratio P2 / P1 provides a gas barrier film characterized by 0 ≦ P2 / P1 ≦ 1.

In the present invention, an organic film is preferably formed between the substrate and the gas barrier film.
The silicon oxide preferably has an oxidation degree of 1 to 2. The substrate is made of, for example, PET or PEN.
The gas barrier film is formed by, for example, a vacuum deposition method. In this case, in the vacuum deposition method, for example, SiO or SiO ₂ is used as a film forming material.
Furthermore, the gas barrier film preferably has a thickness of 10 to 150 nm.

According to the present invention, regarding the infrared absorption spectrum, the peak intensity at 800 to 820 cm ⁻¹ is P1, the peak intensity at 860 to 880 cm ⁻¹ is P2, and the ratio between the peak intensity P1 and the peak intensity P2 is P2 / P1. When a gas barrier film having a ratio P2 / P1 of 0 to 1 is provided, for example, a gas barrier film having a gas barrier performance with a water vapor permeability of 0.1 g / (m ² · day) or less can be obtained.
The gas barrier film of the present invention can be used for barrier films for liquid crystal displays, plasma displays and organic EL displays, food packaging films, solar cell backsheets, and the like.

(A) is typical sectional drawing which shows an example of the gas barrier film which concerns on embodiment of this invention, (b) is typical sectional drawing which shows the other example of the gas barrier film which concerns on embodiment of this invention. is there. It is a graph which shows an example of the Fourier-transform infrared absorption spectrum of the gas barrier film | membrane which takes a normalized light absorbency on a vertical axis | shaft and a wave number on a horizontal axis | shaft and has silicon oxide as a main component. It is typical sectional drawing which shows the film-forming apparatus utilized for manufacture of the gas barrier film which concerns on embodiment of this invention. It is a graph which shows the Fourier-transform infrared absorption spectrum of the gas barrier film | membrane of Examples 1, 2 and Comparative Examples 1 and 2, taking the normalized absorbance on the vertical axis and the wave number on the horizontal axis.

Below, based on the preferred embodiment shown in an accompanying drawing, the gas barrier film of the present invention is explained in detail.
FIG. 1A is a schematic cross-sectional view showing an example of a gas barrier film according to an embodiment of the present invention, and FIG. 1B is a schematic cross-section showing another example of a gas barrier film according to an embodiment of the present invention. FIG.

A gas barrier film 100 shown in FIG. 1A includes a substrate Z and a gas barrier film 102 formed on a surface Zf of the substrate Z. The gas barrier film 102 has a gas barrier function that suppresses permeation of gases such as oxygen and water vapor, and is mainly composed of silicon oxide.
In the gas barrier film 100, the substrate Z is not particularly limited, and various films on which a known gas barrier film is formed can be used.
Specifically, the substrate Z is made of an organic material such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene, polypropylene, polystyrene, polyamide, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyimide, polyacrylate, polymethacrylate. A sheet-like plastic film (resin film) can be used.
In addition, if the form of the board | substrate Z is a film form, the size will not be specifically limited, For example, from the sheet-like thing about 1 m in length to several dozen m and several hundred m It may be long.

Although the thickness of the board | substrate Z is not specifically limited, For example, it is 10-300 micrometers. In particular, when a resin film having a glass transition temperature of 130 ° C. or lower is used as the substrate Z, it is preferable to use the substrate Z having a thickness of 10 to 150 μm from the viewpoint of mechanical strength and transparency.
Moreover, when using a gas barrier film for the back sheet | seat of a solar cell, it is preferable that the thickness of the board | substrate Z is about 300 micrometers from a viewpoint of withstand voltage property.
If the thickness of the substrate Z is less than 10 μm, the mechanical strength of the gas barrier film may be insufficient depending on the type of the substrate Z.
On the other hand, when the thickness of the substrate Z exceeds 150 μm, the transparency of the gas barrier film becomes dominant, and the transparency of the substrate Z becomes dominant, and the gas barrier film has sufficient transparency even if the transparency of the gas barrier film is high. A gas barrier film may not be obtained. Furthermore, it is disadvantageous in terms of flexibility. In addition, since the organic EL display and the liquid crystal display are required to be transparent, further thinner and lighter, it is not preferable to increase the thickness of the substrate Z more than necessary. From the point of view, the thickness range of the substrate is preferable in terms of reducing the thickness and weight of the gas barrier film while ensuring sufficient strength. Considering the above points, the thickness of the substrate Z is preferably 25 to 100 μm.

  In the present invention, for example, a plastic film that can also be used as the substrate Z is used as a base material, on which a protective layer, an adhesive layer, a light reflecting layer, a light shielding layer, a planarizing layer, a buffer layer, a stress, A substrate on which layers (films) for obtaining various functions such as a relaxation layer are formed may be used as the substrate. As will be described later, a substrate (see FIG. 1B) in which the organic layer 104 is formed on the surface Zf of the substrate Z may be used. Alternatively, a substrate in which a plurality of layers of films are formed on a substrate may be used as the substrate.

As described above, the gas barrier film 102 is mainly composed of silicon oxide and is composed of a SiOx film. Here, x represents the degree of oxidation, and when x is 1, it becomes a SiO film, and when x is 2, it becomes a SiO ₂ film. In the SiOx film, when x is 1.0 to 1.4, gas barrier properties are high, and therefore x is preferably 1.0 to 1.4.

The thickness of the gas barrier film 102 is not particularly limited, and may be appropriately determined according to the required gas barrier properties, but is preferably 10 to 150 nm.
By setting the thickness of the gas barrier film 102 to 10 nm or more, a sufficient gas barrier property can be stably secured. In addition, the gas barrier property is basically preferably that the gas barrier film 102 is thicker, but even if the gas barrier film 102 having a thickness exceeding 150 nm is formed, it is difficult to obtain a gas barrier property higher than this. By setting the thickness to 150 nm or less, cracking of the gas barrier film 102 and the like can be suitably prevented, and a preferable result is obtained.
Further, the thickness of the gas barrier film 102 is more preferably 20 to 80 nm in that the above advantages can be obtained more suitably.

In the present invention, the gas barrier film 102 has an infrared absorption characteristic defined based on an infrared absorption spectrum as shown below. FIG. 2 shows an example of the infrared absorption spectrum A of the gas barrier film 102.
In the gas barrier film 102, out of the infrared absorption spectrum A shown in FIG. 2, the peak intensity is P1 in the area alpha ₁ in 800～820Cm ^-1, a peak intensity in the region alpha ₂ of 860~880cm ^-1 P2 When the ratio between the peak intensity P1 and the peak intensity P2 is P2 / P1, the ratio P2 / P1 is 0 ≦ P2 / P1 ≦ 1. The ratio P2 / P1 is preferably 0.45 to 0.90, and more preferably 0.60 to 0.88.
Hereinafter, the gas barrier layer 102, the reason for using the area alpha ₁ peak intensity P1 of 800～820Cm ^-1, reason for using the peak intensity P2 in the area alpha ₂ in 860～880Cm ^-1, and the ratio P2 / P1 of 0 ≦ P2 The reason why / P1 ≦ 1 will be described.

The gas barrier film 102 is defined using the peak intensity P2 in the wavelength range of 860 to 880 cm ⁻¹ .
Here, the wavelength range of the first peak of silicate is 1040 to 1080 cm ⁻¹ , and the wavelength range of the second peak of silicate is 750 to 950 cm ⁻¹ . This is described, for example, in “Film Analysis and Evaluation Technology”, Information Technology Corporation, 2003, p22. It is considered that the wavelength range (1040 to 1080 cm ⁻¹ ) of the first peak of the silicate overlaps with the peak of SiO.
As described above, 860 to 880 cm ⁻¹ that defines the gas barrier film 102 is derived from the silicate, and includes the second peak of the silicate.

As a result of intensive studies by the inventor of the present application, the smaller peak intensity P2 at 860 to 880 cm ⁻¹ does not depend on the composition of the SiOx film containing silicon oxide as a main component, and the water vapor transmission rate is, for example, 0.1 (m ^2. day) It was found that the following high gas barrier performance was obtained and the gas barrier performance was improved. For this reason, the peak intensity P2 in the wavelength range of 860 to 880 cm ⁻¹ was used as an index of gas barrier performance. In addition, from the above-mentioned, it is preferable that the peak intensity P2 of 860-880 cm < ^-1 > is small.

Furthermore, as a result of intensive studies by the inventor of the present application, it has been found that there is a correlation between the peak intensity P2 of 860 to 880 cm ^{−1 and} the peak intensity P1 of 800 to 820 cm ⁻¹ that serve as an index of gas barrier performance. That is, the peak intensity P2 of 860～880Cm ^-1, when assumed to the peak intensity P1 of 800～820Cm ^-1, was found that it is possible to appropriately evaluate the gas barrier performance such as water vapor permeability. Therefore, the gas barrier layer 102, relative to the peak intensity P1 of 800～820Cm ^-1, defines the peak intensity P2 of 860~880cm ^-1. Moreover, the peak intensity P2 of 860～880Cm ^-1, since it is smaller, as described above, and less peak intensity P1 of 800~820cm ^-1. Thus, the ratio P2 / P1 was defined as 0 ≦ P2 / P1 ≦ 1.

In the present embodiment, the gas barrier film 102 has a ratio P2 / P1 defined based on the infrared absorption spectrum of 0 to 1, and the gas barrier film 102 does not contain silicate or contains silicate. Even if the amount is small. In this way, in the gas barrier film 102, the infrared absorption characteristics are defined, and the amount of silicate having absorption of 860 to 880 cm ⁻¹ is reduced, so that it depends on the composition of the SiOx film mainly composed of silicon oxide. For example, even if the value of x is not in the above-described preferable range, for example, a high gas barrier performance with a water vapor transmission rate of 0.1 (m ² · day) or less can be obtained.

The infrared absorption spectrum A of the gas barrier film 102 is measured using, for example, FT-IR (Fourier transform infrared spectrophotometer). The measurement method by this FT-IR is not particularly limited, and for example, a transmission method, a reflection method, or a total reflection method (ATR method) can be used.
The above-described peak intensity P1 and peak intensity P2 of the gas barrier film 102 are measured in a state where the gas barrier film 102 is formed on the substrate 100, or in a state where the gas barrier film 102 is formed on a predetermined substrate such as a silicon substrate. Measured. When the gas barrier film 102 is formed on a silicon substrate or the like, if the gas barrier film 102 is formed on the surface Zf of the substrate Z under the deposition conditions of the gas barrier film 102 when forming the silicon substrate or the like, a gas barrier having a ratio P2 / P1. A film 102 can be obtained.

In the present invention, it is not limited to the configuration of the gas barrier film 100 shown in FIG. 1A, but between the substrate Z and the gas barrier film 102 as in the gas barrier film 100a shown in FIG. In addition, an organic film 104 may be formed. As in the gas barrier film 100a, the organic film 104 is formed on the surface Zf of the substrate Z, and the gas barrier film 102 is formed on the surface 104a of the organic film 104, whereby unevenness existing on the surface Zf of the substrate Z is formed. The film formation surface of the gas barrier film 102 can be flattened. Thereby, the outstanding gas barrier performance which the gas barrier film 102 has can fully be expressed. Moreover, as described above, the gas barrier film 102 has a ratio P2 / P1 of 0 to 1, and an excellent gas barrier performance with respect to the water vapor transmission rate and the like can be obtained regardless of the composition of the SiOx film. Therefore, the gas barrier film 100a has better gas barrier performance.
The gas barrier films 100 and 100a described above can be used for barrier films for liquid crystal displays, plasma displays and organic EL displays, food packaging films, solar cell backsheets, and the like.

In the present invention, the material (main component) for forming the organic film 104 of the gas barrier film 100a is not particularly limited, and various known organic substances (organic compounds) can be used. Organic polymer compounds) are preferable examples.
Examples include TMPTA (trimethylolpropane triacrylate), epoxy resin, acrylic resin, methacrylic resin, polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, poly Examples include ether imide, cellulose acylate, polyurethane, polyether ketone, polycarbonate, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, and fluorene ring-modified polyester.

Further, the method for forming the organic film 104 is not particularly limited, and all known methods for forming an organic film can be used.
As an example, a paint prepared by dissolving (dispersing) an organic substance, an organic monomer, or a polymerization initiator in a solvent is applied to the substrate Z by a known application means such as a roll coat, a gravure coat, or a spray coat. Examples of the coating method include drying, drying, and curing by heating, ultraviolet irradiation, electron beam irradiation, or the like, if necessary. Also, the organic material or the same paint as in the coating method is evaporated, the vapor is attached to the substrate Z, cooled / condensed to form a liquid film, and the film is cured by ultraviolet rays or electron beams. A flash vapor deposition method in which film formation is performed can be suitably used. Also, a transfer method for transferring the organic film 104 formed into a sheet shape can be used.

In the present invention, the thickness of the organic film 104 is not particularly limited, and may be set as appropriate according to the surface property and thickness of the substrate Z, the required gas barrier property, and the like. 3-5 micrometers is preferable.
By setting the thickness of the organic film 104 within the above range, the unevenness existing on the surface of the substrate Z can be more reliably embedded, and the deposition surface of the gas barrier film 102 can be suitably flattened. It is preferable in terms of improving adhesion.
Note that in the present invention, the organic film 104 is not limited to be formed of a single organic film, and the organic film 104 may be formed of a plurality of organic films. For example, an organic film formed by flash vapor deposition may be provided on an organic film formed by a coating method, and the organic film 104 may be formed using the two organic films.

In the present invention, the gas barrier film 102 of the gas barrier film 100 shown in FIG. 1A and the gas barrier film 102 of the gas barrier film 100a shown in FIG. 1B are formed using, for example, the film forming apparatus shown in FIG. be able to. Hereinafter, a film forming apparatus and a film forming method for the gas barrier film 102 will be described.
As described above, the gas barrier film 102 is a SiOx film containing silicon oxide as a main component, and the ratio P2 / P1 is 0-1. Such a gas barrier film 102 is formed on the film-forming material M as described later in an atmosphere before the gas barrier film 102 is formed, for example, in an atmosphere having a pressure of 1 × 10 ⁻³ Pa or less and a water pressure of 6 × 10 ⁻⁴ Pa or less. It can be formed by a vacuum evaporation method using SiO or SiO ₂ . Note that when the gas barrier film 102 is formed, the conditions for the ratio P2 / P1 to be 0 to 1 may be obtained in advance, and therefore the film formation conditions are limited to the above-described pressure and moisture pressure conditions. It is not a thing.

  A film forming apparatus 10 shown in FIG. 3 is a roll-to-roll type film forming apparatus, and is supplied through a predetermined path from the supply chamber 12 to the winding chamber 16 through the film forming chamber 14. For example, the gas barrier film 102 is continuously formed on the surface Zf of the long substrate Z (see FIG. 1A) while being conveyed from the chamber 12 to the winding chamber 16 through the long substrate Z, and the gas barrier film 100 (See FIG. 1 (a)).

The film forming apparatus 10 basically includes a supply chamber 12 for supplying a substrate Z, a film forming chamber (chamber) 14 for forming a gas barrier film 102 (see FIG. 1A) on the substrate Z, and a gas barrier film 102 ( The substrate Z on which the substrate Z (refer to FIG. 1A), that is, the gas barrier film 100 is wound up, the vacuum chamber 32, and the controller 36 are included. The operation of each element in the film forming apparatus 10 is controlled by the control unit 36.
In the film forming apparatus 10, a slit-like opening 15 c through which the substrate Z passes is formed on a wall 15 a that partitions the supply chamber 12 and the film forming chamber 14. 16 is formed with a slit-shaped opening 15c through which the substrate Z (gas barrier film 100) on which the gas barrier film 102 is formed passes.

  In the film forming apparatus 10, a vacuum exhaust unit 32 is connected to the supply chamber 12, the film forming chamber 14, and the winding chamber 16 through a pipe 34. The inside of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 is brought to a predetermined degree of vacuum (pressure) by the evacuation unit 32. The pipe 34 may be provided with a valve (not shown) in the vicinity of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 so that the exhaust amount of each chamber by the vacuum exhaust unit 32 can be adjusted.

The evacuation unit 32 evacuates the supply chamber 12, the film formation chamber 14, and the take-up chamber 16, and maintains a predetermined degree of vacuum (predetermined pressure). A vacuum pump such as a dry pump or a turbo molecular pump is provided. It is what you have. The supply chamber 12, the film formation chamber 14, and the winding chamber 16 are each provided with a pressure sensor (not shown) for measuring the internal pressure. Further, the film forming chamber 14 is provided with, for example, a vacuum partial pressure gauge (not shown) in order to measure the internal water pressure (H ₂ O partial pressure).
In addition, the ultimate vacuum degree of the supply chamber 12 and the winding chamber 16 by the evacuation unit 32 is not particularly limited, and the film formation chamber 14 has a film formation condition for the gas barrier film 102 as described later. A sufficient degree of vacuum may be maintained. The evacuation unit 32 is controlled by the control unit 36. Each pressure sensor and vacuum partial pressure gauge are also connected to the control unit 36, and the pressure and moisture pressure (H ₂ O partial pressure) obtained by each pressure sensor and vacuum partial pressure gauge are stored in the control unit 36. .

The supply chamber 12 is a part that supplies the substrate Z, and is provided with a rotating shaft 20 and a guide roller 21.
The rotating shaft 20 feeds the substrate Z continuously. A substrate roll 20 a in which the substrate Z is wound counterclockwise is loaded on the rotary shaft 20.
For example, a motor (not shown) is connected to the rotary shaft 20 as a drive source. Rotary shaft 20 is rotated in a direction r ₁ rewinding the substrate Z by the motor, in the present embodiment, is rotated clockwise, the substrate Z is continuously fed from the substrate roll 20a.

The guide roller 21 guides the substrate Z to the film forming chamber 14 through a predetermined transport path. The guide roller 21 is a known guide roller.
In the film forming apparatus 10 of the present embodiment, the guide roller 21 may be a driving roller or a driven roller. Further, the guide roller 21 may be a roller that acts as a tension roller that adjusts the tension when the substrate Z is transported.

  As will be described later, the winding chamber 16 is a portion of the film forming chamber 14 where the substrate Z on which the gas barrier film 102 is formed on the surface Zf is wound, and the winding shaft 30 and the two guide rollers 31a and 31b are provided. Is provided.

The winding shaft 30 is for winding the substrate Z on which the gas barrier film 102, which is the gas barrier film 100, is formed in a roll shape, for example, clockwise.
For example, a motor (not shown) is connected to the winding shaft 30 as a drive source. The take-up shaft 30 is rotated by this motor, and the substrate Z on which the gas barrier film 102 is formed is taken up.
In the winding shaft 30, the substrate Z on which the gas barrier film 102 is formed is rotated by the motor in the direction r ₂ of winding, and in this embodiment, the substrate Z is rotated clockwise to form the gas barrier film 102. Are continuously wound up, for example, clockwise to obtain the substrate roll 30a of the gas barrier film 100.

The guide rollers 31a and 31b guide the substrate Z transported from the film forming chamber 14 to the winding shaft 30 through a predetermined transport path. The guide rollers 31a and 31b are constituted by known guide rollers. As with the guide roller 21 in the supply chamber 12, the guide rollers 31a and 31b may be drive rollers or driven rollers. The guide rollers 31a and 31b may be rollers that act as tension rollers.
In the film forming apparatus 10, the feeding of the substrate Z from the substrate roll 20 a and the winding of the substrate Z on the winding shaft 36 of the winding chamber 16 are performed in synchronization, and the substrate Z is moved in the longitudinal direction along a predetermined transport path. The gas barrier film 102 is formed on the substrate Z in the film forming chamber 14.

The film forming chamber 14 functions as a vacuum chamber, and is made of a material used in various vacuum chambers such as stainless steel, aluminum, or aluminum alloy. The film forming chamber 14 is a portion where the gas barrier film 102 is continuously formed on the surface Zf of the substrate Z by, for example, vacuum deposition while transporting the substrate Z.
Note that the film formation chamber 14 may be provided with a gas introduction means for introducing argon gas for adjusting the degree of vacuum. The gas introduction means includes or is connected to a connection means with a cylinder or the like, a gas flow rate adjustment means, or the like. As the gas introduction means, a known one used in a vacuum deposition apparatus is used.

In the film forming chamber 14, six guide rollers 24a, 24b, 25, 27, 28a, 28b, a drum 26, a film forming unit 40, and a vapor deposition unit 50 are provided.
The guide rollers 24a and 24b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28a and 28b are provided in this order from the upstream side to the downstream side in the transport direction D. That is, the guide rollers 24a and 24b and the guide roller 25 are provided on the upstream side with respect to the drum 26, and the guide roller 27 and the guide rollers 28a and 28b are provided on the downstream side.

The guide rollers 24a and 24b and the guide rollers 28a and 28b are arranged in parallel so as to face each other with a predetermined interval. The guide rollers 24 a and 24 b and the guide rollers 28 a and 28 b are arranged with their longitudinal directions orthogonal to the conveyance direction D of the substrate Z.
Further, the guide roller 25 and the guide roller 27 are arranged in parallel so as to face each other at a distance narrower than the distance between the guide roller 24 and the guide roller 28. The guide roller 25 and the guide roller 27 are arranged so that the longitudinal direction thereof is orthogonal to the transport direction D of the substrate Z.

The guide rollers 24 a and 24 b and the guide roller 25 are for transporting the substrate Z transported from the guide roller 21 provided in the supply chamber 12 to the drum 26. The guide rollers 24a and 24b and the guide roller 25 have, for example, a rotation axis in a direction orthogonal to the transport direction D of the substrate Z (hereinafter referred to as an axial direction) and can rotate, and the guide rollers 24a and 24b and the guide roller 25 The length of the roller 25 in the axial direction is longer than the length in the width direction orthogonal to the longitudinal direction of the substrate Z (hereinafter referred to as the width of the substrate Z).
The rotating shaft 20, the guide roller 21, the guide rollers 24a and 24b, and the guide roller 25 constitute a first transport unit of the present invention.

The guide roller 27 and the guide rollers 28 a and 28 b convey the substrate Z wound around the drum 26 to a guide roller 31 a provided in the winding chamber 16. For example, the guide roller 27 and the guide rollers 28a and 28b have a rotation shaft in the axial direction and are rotatable, and the guide roller 27 and the guide rollers 28a and 28b are longer in the axial direction than the width of the substrate Z. Also long.
The guide roller 27, the guide roller 28, the guide rollers 31a and 31b, and the take-up shaft 30 constitute the second conveying means of the present invention.
The six guide rollers 24a, 24b, 25, 27, 28a, and 28b have the same configuration as the guide roller 21 provided in the supply chamber 12 except for the above configuration, and thus detailed description thereof is omitted.

The drum 26 is provided below the space H between the guide rollers 24b and 25 and the guide rollers 27 and 28a. The drum 26 is arranged with its longitudinal direction parallel to the longitudinal direction of the four guide rollers 24b, 25, 27, 28a. The drum 26 is longer in the axial direction (longitudinal direction) than the width of the substrate Z.
The drum 26 has, for example, a cylindrical shape, and cylindrical support portions 29 are provided on both end surfaces thereof. The support portion 29 is rotatably supported by, for example, a bearing (not shown) provided on the wall surface (not shown) of the film forming chamber 14. As a result, the drum 26 rotates in the rotation direction ω around the rotation axis C.
The substrate Z is wound around the surface 26a (circumferential surface) of the drum 26, and the drum 26 rotates in the rotation direction ω, so that the substrate Z is held in a predetermined film formation position and the substrate Z is moved in the transport direction D. It is to be transported.

  In addition, about the drum 26, when the thickness of the board | substrate Z is thin, it is preferable to cool in order to prevent the board | substrate Z being cut | disconnected by the heat | fever at the time of film-forming. However, since the temperature of the drum 26 affects the film quality of the gas barrier film 102, the temperature of the drum 26 is appropriately determined according to the thickness of the substrate Z, the film quality of the gas barrier film 102 to be formed, and the like.

  As shown in FIG. 3, the film forming unit 40 is provided so as to face the lower side of the drum 26, and in a state where the substrate Z is wound around the drum 26, the drum 26 rotates and the substrate Z is conveyed. The gas barrier film 102 is formed on the surface Zf of the substrate Z while being transported in the direction D.

The film forming unit 40 forms the gas barrier film 102 by, for example, a vacuum deposition method. The film forming unit 40 includes a heating container 42, a heater 44, a temperature sensor 45, a first temperature adjusting unit 46, a pair of partition plates 48, and a shutter 49.
The partition plate 48 divides the heating container 42 in the film forming chamber 14, and the pair of partition plates 48 are arranged so as to sandwich the heating container 42.

The heating container 42 is a hollow container whose upper surface is open, and has, for example, a rectangular casing. A plurality of the heating containers 42 are provided along the axial direction (longitudinal direction) of the drum 26.
Each heating container 42 is filled with a film forming material M for forming the gas barrier film 102 therein, for example, in the form of pellets. In the present embodiment, the film forming material M is mainly composed of silicon oxide, and is, for example, SiO or SiO ₂ .

  Each heating container 42 is formed of a material that does not react with the film-forming material M, has sufficient heat resistance, and has good thermal conductivity, like a general vacuum evaporation crucible. For example, it is formed of various metals or alloys or various ceramics. The material of the heating container 42 is appropriately selected according to the composition, melting point, etc. of the film forming material M.

Moreover, it does not specifically limit to the shape of the heating container 42, The container of various shapes can be utilized.
The heating container 42 preferably has a shape such as a cylindrical shape such as a cylindrical shape or a rectangular shape that does not vary in cross section in a direction perpendicular to the vertical direction of the cylinder. By making the heating container 42 into such a cylindrical shape, the area of the evaporation surface does not change even if the film forming material to be filled evaporates and the liquid level (evaporation surface) is lowered. This is preferable in terms of stabilizing the amount, that is, the film forming rate, and stabilizing the directivity of the film forming material vapor.

  The heater 44 heats the heating container 42 to a predetermined temperature and melts the film forming material M inside the heating container 42. A heater 44 is provided so as to surround the periphery of the wall surface of the heating container 42. The heater 44 is connected to the first temperature adjustment unit 46.

  The configuration of the heater 44 is not particularly limited. Various types of heaters such as a heating wire, a resistor heater such as a conductor, and a sheath heater can be used, and are appropriately selected according to the melting point of the film forming material M and the like.

  The first temperature adjusting unit 46 applies a voltage, current, power, or the like applied to each heater 44 according to the temperature at which the heating container 42 is heated, that is, the set temperature that is sufficient to evaporate the film forming material M. It is for adjusting. The first temperature adjustment unit 46 is connected to the control unit 36.

  The temperature sensor 45 is provided, for example, at the top of each heating container 42 and is constituted by a thermocouple. Each temperature sensor 45 is connected to the control unit 36 although not shown. Depending on the set temperature and the temperature measured by the temperature sensor 45 by the control unit 36, for example, each heater 44 from the first temperature adjustment unit 46 so that the temperature in the heating container 42 becomes the set temperature by feedback control. The voltage, current or power supplied to the is controlled.

The film forming unit 40 is provided with a shutter 49 that blocks the vapor of the film forming material M from the opening of the heating container 42. The shutter 49 is composed of a plate-like member that blocks the vapor of the film forming material M from the opening of the heating container 42 and has a size that covers the entire opening of the heating container 42. The shutter 49 is connected to a rotation support shaft (not shown), and a motor (not shown) is connected to the rotation support shaft. By this motor, the shutter 49 is rotated via the rotation support shaft, the upper part of the opening of the heating container 42 is opened, and the vapor of the film forming material M reaches the surface Zf of the substrate Z.
The motor is also connected to the control unit 36, and the control unit 36 controls the rotation thereof, that is, the blocking of the vapor of the film forming material M from the opening of the heating container 42 by the shutter 49.

The vapor deposition part 50 vapor-deposits the metal m which has a function which adsorb | sucks moisture on things other than the board | substrate Z by a vacuum vapor deposition method. In this embodiment, the vapor deposition part 50 vapor-deposits the metal m which has the function to adsorb | suck a water | moisture content to the mask 59, for example. The metal m having a function of adsorbing moisture is, for example, Al or Ti.
The vapor deposition unit 50 includes a heating container 52, a heater 54, a temperature sensor 55, a second temperature adjustment unit 56, a pair of partition plates 58, and a mask 59. It is the same composition as. However, the vapor deposition unit 50 is different from the film forming unit 40 in that at least one heating container 52 is sufficient.
The partition plate 58 partitions the heating container 52 in the film forming chamber 14, and the pair of partition plates 58 are arranged so as to sandwich the heating container 52.

  Since the heating container 52, the heater 54, and the temperature sensor 55 of the vapor deposition unit 50 have the same configuration as the heating container 42, the heater 44, and the temperature sensor 45 of the film forming unit 40, detailed descriptions thereof are omitted. In the vapor deposition section 50, the heating container 52 is filled with, for example, Al or Ti as a metal m having a function of adsorbing moisture in the form of pellets. The heater 54 is connected to the second temperature adjustment unit 56. The heater 54 is also appropriately selected according to the melting point of the metal m, like the heater 44 of the film forming unit 40.

The second temperature adjustment unit 56 adjusts the voltage, current, power, or the like applied to the heater 54 according to the temperature at which the heating container 52 is heated, that is, the set temperature that is sufficient to evaporate the metal m. Is for. The second temperature adjustment unit 56 is also connected to the control unit 36, and the temperature sensor 55 is also connected to the control unit 36 although not shown.
According to the set temperature and the temperature measured by the temperature sensor 55 by the control unit 36, the heater 54 is supplied from the second temperature adjustment unit 56 so that the temperature in the heating container 52 becomes the set temperature by feedback control, for example. The voltage, current or power supplied to the is controlled.

The vapor deposition section 50 is provided with a mask 59 above the opening of the heating container 52. Al or Ti is deposited on the mask 59. The moisture in the film forming chamber 14 is adsorbed by the Al or Ti vapor, and the water pressure in the film forming chamber 14 can be set to 6 × 10 ⁻⁴ Pa or less, for example. The moisture pressure in the film forming chamber 14 is preferably 6 × 10 ⁻⁴ Pa or less before the gas barrier film 102 is formed, for example. This moisture pressure (6 × 10 ⁻⁴ Pa) corresponds to 60% or less of the total pressure in the film forming chamber 14.
In addition, the water pressure in the film forming chamber 14 is preferably 3 × 10 ⁻³ Pa or less during the formation of the gas barrier film 102, for example. This moisture pressure (3 × 10 ⁻³ Pa) corresponds to 30% or less of the total pressure in the film forming chamber 14.
Since Al or Ti for adsorbing moisture described above is deposited on the mask 59 other than the substrate Z, the vapor of Al or Ti does not scatter in the film forming chamber 14 and adheres to the substrate Z as a foreign substance. There is nothing.
The vapor deposition by the vapor deposition section 50 is not limited to the mask 59, and the vapor deposition position is not particularly limited as long as it does not adversely affect the formation of the gas barrier film 102 at a place other than the surface Zf of the substrate Z. It is not something.

In the film forming apparatus 10, the vapor deposition unit 50 is provided in the region α on the upstream side of the drum 26 in the film forming chamber 14. However, the present invention is not limited to this. It may be provided in the region β on the downstream side of the drum 26. When vapor deposition is performed before film formation, it is preferably provided in the upstream region α where the substrate Z is transported. When vapor deposition is performed during film formation after the start of film formation, the substrate Z after film formation is provided. Is preferably provided in the downstream region β where the toner is conveyed.
Further, the film chamber 14 may be disposed in both the upstream region α and the downstream region β of the drum 26. In this case, both of them may be vapor-deposited at the same time. The film in the upstream region α is vapor-deposited before the film formation, and the film in the downstream region β is vapor-deposited after the film formation is started. You may switch things.
Further, the number of heating containers 52 of the vapor deposition section 50 is not particularly limited, and the volume of the film formation chamber 14, the thickness and type of the substrate, the thickness and type of the organic film, and the film formation conditions of the gas barrier film 102. Depending on the case, it is appropriately selected.

In addition, although the heating method of the heating container 42 of the film forming unit 40 is a heating method, if the gas barrier film 102 can be formed by evaporating the film forming material M such as SiO or SiO ₂ , the heating method is There is no particular limitation. As a heating method, a resistance heating method in which a current is applied to the film forming material M to generate heat, an electromagnetic induction heating method, an electron beam beam heating method, a laser heating method, or the like can be used.
Also, in the evaporation unit 50, if the metal m having a function of adsorbing moisture, for example, Al or Ti, can be evaporated, the heating method is limited to the heating method by the heater as in the film forming unit 40. There is nothing, and the various heating methods described above similar to those of the film forming unit 40 can be used.

Next, a method for forming the gas barrier film 102 by the film forming apparatus 10 will be described.
In the film forming apparatus 10, for example, the substrate Z is transported to the film forming chamber 14 through the guide roller 21 from the substrate roll 20 wound counterclockwise. In the film forming chamber 14, the film is conveyed to the winding chamber 16 through the guide rollers 24 a and 24 b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28 a and 28 b. In the winding chamber 16, the substrate Z is wound around the winding shaft 30 through the guide rollers 31 a and 31 b. Thus, after passing the substrate Z through this transfer path, the inside of the supply chamber 12, the film formation chamber 14, and the winding chamber 16 is brought to a predetermined degree of vacuum by the vacuum exhaust unit 32.

Thereafter, while the temperature of the heating container 52 is monitored by the temperature sensor 55 by the control unit 36, the heating container 52 is heated to a predetermined temperature while adjusting the voltage, current, and the like applied from the second temperature adjusting unit 56 to the heater 54. Then, in the vapor deposition section 50, Al or Ti is melted and evaporated to deposit Al or Ti on the mask 59. At this time, Al or Ti vapor is deposited on the mask 59 while adsorbing moisture in the film forming chamber 14. Thereby, the water pressure in the film forming chamber 14 can be set to 6 × 10 ⁻⁴ Pa or less, for example.
In the film forming chamber 14, for example, before the gas barrier film 102 is formed, the water pressure in the film forming chamber 14 is preferably 6 × 10 ⁻⁴ Pa or less. At this time, the pressure in the film forming chamber 14 is preferably 1 × 10 ⁻³ Pa or less.
After the pressure in the film forming chamber 14 and the water pressure reach the above-described pressures, the controller 36 stops the heating of the heater 54 by the second temperature adjusting unit 56, and the deposition unit 50 deposits Al or Ti. Stop.

Next, while the temperature of the heating container 42 is monitored by the temperature sensor 45 by the control unit 36, the heating container 42 is brought to a predetermined temperature while adjusting the voltage, current, etc. applied to the heater 44 from the first temperature adjustment unit 46. Heating is performed, and the film forming material M such as SiO or SiO ₂ is melted and evaporated in the film forming unit 40.

  Next, the control unit 36 rotates the shutter 49 to open the opening of the heating container 42, and the vapor of the film forming material M reaches the surface Zf of the substrate Z. In such a state, the substrate Z is wound at a predetermined transport speed while the substrate Z is held at the position where the vapor of the film forming material M reaches by the drum 26, and the film forming material M is applied to the surface Zf of the substrate Z. Is vapor-deposited. As a result, the gas barrier film 102 having a ratio P2 / P1 of 0 to 1 is formed as the gas barrier film 102.

When SiO is used as the film forming material M for vapor deposition by the film forming unit 40, the gas barrier film 102 with a ratio P2 / P1 of 0 to 1 can be obtained, and the SiO vapor deposition is performed in an atmosphere with a low moisture pressure. Therefore, the oxidation of SiO is suppressed, and the SiOx film formed as the gas barrier film 102 has an oxidation degree as small as 1.0 to 1.4, for example. Thereby, the gas barrier film | membrane 102 excellent in gas barrier performance is obtained. As a result, the gas barrier film 100 having high gas barrier performance can be obtained.
Even when SiO ₂ is used as the film forming material M for vapor deposition by the film forming unit 40, a gas barrier film 102 having an excellent gas barrier performance with a ratio P2 / P1 of 0 to 1 can be obtained as in the case of using SiO. The gas barrier film 100 having high gas barrier performance can be obtained.

  Then, the rotating shaft 20 is sequentially rotated clockwise by a motor, and the substrate Z is continuously fed out. The drum 26 is held at a position where the SiO vapor reaches the drum 26, and the drum 26 is moved at a predetermined speed. The gas barrier film 102 is continuously formed on the surface Zf of the substrate Z so as to have a predetermined film thickness by being rotated. Then, the substrate Z on which a predetermined film is formed on the surface Zf, that is, the gas barrier film 100 is wound around the winding shaft 30 through the guide rollers 28a and 28b and the guide rollers 31a and 31b, and finally, the gas barrier film 100 Can be obtained.

Note that vapor deposition by the vapor deposition unit 50 is not limited to before the gas barrier film 102 is formed. For example, vapor deposition by the vapor deposition unit 50 may be performed after the gas barrier film 102 starts to be formed, and further, vapor deposition by the vapor deposition unit 50 may be performed even after the gas barrier film 102 has been formed before the gas barrier film 102 is formed. You may go.
When vapor deposition is performed in the vapor deposition section 50 after the gas barrier film 102 is formed, that is, when vapor deposition is performed in the vapor deposition section 50 during the formation of the gas barrier film 102, the moisture pressure in the film deposition chamber 14 is set to 3 × 10 ^−. It is preferable that the pressure is ³ Pa or less and the pressure in the film forming chamber 14 is 1 × 10 ⁻² Pa or less. At this time, the control unit 36 appropriately heats the heater 54 by the second temperature adjusting unit 56 so that the pressure and moisture pressure are within the ranges described above, and causes the vapor deposition unit 50 to appropriately deposit Al or Ti. In this state, the gas barrier film 102 is formed as described above.
When vapor deposition is performed by the vapor deposition section 50 during the formation of the gas barrier film 102, the pressure and moisture pressure in the film formation chamber 14 before the gas barrier film 102 is formed are not particularly limited.

Furthermore, vapor deposition is performed in the vapor deposition section 50 before the gas barrier film 102 is formed and also during the gas barrier film 102 is formed, and the moisture pressure in the film formation chamber 14 is 6 × 10 ⁻⁴ Pa or less before the gas barrier film 102 is formed. As described above, the pressure is 1 × 10 ⁻³ Pa or less, the moisture pressure in the film forming chamber 14 is 3 × 10 ⁻³ Pa or less, and the pressure is 1 × 10 ⁻² Pa or less during the formation of the gas barrier film 102. Alternatively, a gas barrier film 102 may be formed.

Even in the case of vapor deposition by the vapor deposition unit 50 during the film formation after the gas barrier film 102 starts to be formed, and vapor deposition by the vapor deposition unit 50 after the gas barrier film 102 starts to be formed before the gas barrier film 102 is formed, the above-mentioned As described above, the gas barrier film 102 has a ratio P2 / P1 of 0 to 1, and the formed SiOx film has a small oxidation value of x = 1.0 to 1.4, and has a high gas barrier performance. A film 100 can be obtained.
Even when the gas barrier film 102 is formed using SiO ₂ , an SiO ₂ film having a ratio P2 / P1 of 0 to 1 can be obtained as the gas barrier film 102.

When vapor deposition is performed by the vapor deposition unit 50 after film formation is started by the film formation unit 40, even if moisture is released from the substrate Z transported into the film formation chamber 14, the moisture is converted into Al or Ti vapor. Since water is adsorbed, the water pressure can be kept below a predetermined value even during film formation. For this reason, when SiO is used as the film forming material M, it is possible to suppress oxidation that occurs after the SiO is deposited on the surface Zf of the substrate Z. In particular, when vapor deposition is performed by the vapor deposition unit 50 before the gas barrier film 102 is deposited and after the gas barrier film 102 is deposited, the SiOx film can be formed in an atmosphere having a low moisture pressure, and the moisture pressure in the deposition chamber 14 can be increased. Since a low atmosphere can be maintained even during film formation, oxidation after SiO deposition is suppressed, and the degree of oxidation of the SiOx film can be further reduced. Thereby, the gas barrier film 100 which has still higher gas barrier performance can be obtained.
In addition, since the amount of moisture in the film formation chamber 14 can be reduced by performing vapor deposition before forming the gas barrier film 102 on the surface Zf of the substrate Z, it is possible to reduce the amount of water in the film formation chamber 14 to a predetermined degree of vacuum. The evacuation time can be shortened, and the deposition cost of the gas barrier film 102 can be reduced.

In the film forming apparatus 10, the film forming unit 40 is formed by a vacuum deposition method, but is not limited to this, and a SiOx film such as SiO or SiO ₂ having a ratio P2 / P1 of 0 to 1 is used. As long as the gas barrier film 102 can be formed, a CVD method may be used. Also in this case, the formation conditions of the SiOx film having the ratio P2 / P1 of 0 to 1 are obtained in advance.
Examples of the CVD method include CCP (Capacitively Coupled Plasma) -CVD, ICP (Inductively Coupled Plasma) -CVD, microwave CVD, ECR (Electron Cyclotron Resonance) -CVD, and atmospheric pressure barrier discharge CVD. Various plasma CVD methods such as can be used.
By forming the gas barrier film 102 using the plasma CVD method, a higher gas barrier property can be obtained, and further, cracking due to the structure inside the film can be suitably prevented, and flexibility can be improved. Can be manufactured with high productivity.

When the gas barrier film 100a shown in FIG. 1B is manufactured, as described above, the substrate Z on which the organic film 104 is formed on the surface Zf is manufactured using the coating method or the flash vapor deposition method. A substrate roll is obtained by winding the substrate Z.
Next, the substrate roll of the substrate Z on which the organic film 104 is formed is set on the rotating shaft 20 of the film forming apparatus 10 shown in FIG.
Then, the substrate 106 is transported from the substrate roll 6 to the film forming chamber 14 via the guide roller 21, and the guide rollers 24 a and 24 b, the guide roller 25, the drum 26, the guide roller 27, and the guide rollers 28 a and 28 b in the film forming chamber 14. Then, the substrate 106 is transferred to the winding chamber 16. In the winding chamber 16, the substrate 106 is wound on the winding shaft 30 through the guide rollers 31 a and 31 b. In this way, after passing the substrate 106 through this transport path, the gas barrier film 102 is formed on the surface 104a of the organic film 104 as described above, and the gas barrier film 100a shown in FIG. 1B is obtained. The method for forming the gas barrier film 102 is the same as the method for forming the gas barrier film 102 on the surface Zf of the substrate Z described above except that it is formed on the surface 104a of the organic film 104. Is omitted.

Even when the gas barrier film 102 is formed on the surface 104 a of the organic film 104, Al or Ti is vapor-deposited on the mask 59 by the vapor deposition unit 50 before the gas barrier film 102 is formed, and the degree of vacuum and moisture pressure according to the film formation conditions After that, the vapor deposition by the vapor deposition unit 50 is stopped, and the formation of the SiOx film by the film forming unit 40 is started.
Even when the substrate Z on which the organic film 104 is formed is used, as in the case where the gas barrier film 102 is formed on the surface Zf of the substrate Z, the ratio P2 / P1 is 0 to 1, and the degree of oxidation is small and the gas barrier film 102 is formed. Can be formed. For this reason, the gas barrier film 100a with small water vapor permeability, oxygen permeability, etc., that is, excellent gas barrier performance can be obtained.
Even in the case of forming a gas barrier film 102 on the surface 104a of the organic film 104 with a SiO _2, can be the ratio P2 / P1 is obtained by the SiO ₂ film 0-1 and the gas barrier layer 102, having a high gas barrier performance A gas barrier film 100a can be obtained.

  The present invention is basically as described above. The gas barrier film of the present invention has been described in detail above. However, the present invention is not limited to the above-described embodiment, and it is needless to say that various improvements or changes may be made without departing from the gist of the present invention. .

Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
In this example, the gas barrier films of Examples 1 and 2 and Comparative Examples 1 and 2 shown below were prepared, and the gas barrier performances of the gas barrier films of Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated. did.
The water vapor transmission rate was used as an index of gas barrier performance of the gas barrier films of Examples 1 and 2 and Comparative Examples 1 and 2.

Example 1
In Example 1, first, an SiO film was formed on a silicon wafer using the EB heating type vacuum deposition apparatus under the film formation conditions of 0 ≦ P2 / P1 ≦ 1 for the gas barrier film. The infrared absorption spectrum of this SiO film was measured using FTIR-6100 manufactured by JASCO Corporation (JASCO). The result is shown in FIG. In Example 1, the ratio P2 / P1 was 0.82.
In Example 1, the pressure was 4 × 10 ⁻⁴ Pa for the film forming conditions. At the same time, in order to lower the residual water pressure, a Meissner coil was used, and the gas partial pressure (water pressure) of water was set to 3 × 10 ⁻⁴ Pa, which was one digit higher than the nitrogen gas partial pressure.
Next, an SiO film having a thickness of 70 nm was formed on a PEN film having a thickness of 100 μm under the film forming conditions for obtaining the value of P2 / P1, and a gas barrier film was obtained.
Next, the water vapor permeability of the gas barrier film of Example 1 was measured using a water vapor permeability measuring apparatus AQUATRAN (registered trademark) manufactured by MOCON under measurement conditions of a temperature of 40 ° C. and a relative humidity of 90%. As a result, it was 0.01 g / (m ² · day).
The PEN film used was Teonex (registered trademark) Q65FA manufactured by Teijin DuPont Films.

(Example 2)
In Example 2, first, an SiO ₂ film was formed on a silicon wafer by using an EB heating type vacuum deposition apparatus under the film formation conditions of 0 ≦ P2 / P1 ≦ 1 for the gas barrier film. The infrared absorption spectrum of this SiO ₂ film was measured in the same manner using the same apparatus as in Example 1. The result is shown in FIG. In Example 2, the ratio P2 / P1 was 0.72.
In Example 2, the pressure was set to 4 × 10 ⁻⁴ Pa for the film forming conditions. At the same time, in order to lower the residual water pressure, a Meissner coil was used, and the gas partial pressure (water pressure) of water was set to 3 × 10 ⁻⁴ Pa, which was one digit higher than the nitrogen gas partial pressure.
Next, a SiO ₂ film having a thickness of 70 nm was formed on a PEN film having a thickness of 100 μm under the film forming conditions that obtain the value of P2 / P1, and a gas barrier film was obtained. In addition, the same thing as Example 1 was used for the PEN film.
Next, the water vapor transmission rate of the gas barrier film of Example 2 was measured in the same manner using the same apparatus as in Example 1. As a result, it was 0.02 g / (m ² · day).

(Comparative Example 1)
In Comparative Example 1, as compared with Example 1, with respect to the film forming conditions, except that the pressure was 1 × 10 ⁻² Pa and the gas partial pressure (water pressure) of water was 8 × 10 ⁻³ Pa, Similar to Example 1, a SiO film was formed on a silicon wafer. The infrared absorption spectrum of this SiO film was measured in the same manner using the same apparatus as in Example 1. The infrared absorption spectrum of Comparative Example 1 is shown in FIG. In Comparative Example 1, the ratio P2 / P1 was 1.21.
Furthermore, a gas barrier film was produced using the same PEN film as in Example 1, and the water vapor transmission rate of the gas barrier film of Comparative Example 1 was measured in the same manner using the same apparatus as in Example 1. As a result, it was 0.5 g / (m ² · day).

(Comparative Example 2)
In Comparative Example 2, as compared with Example 2, with respect to the film forming conditions, except that the pressure was 1 × 10 ⁻² Pa and the gas partial pressure of water (water pressure) was 8 × 10 ⁻³ Pa, Similar to Example 2, a SiO ₂ film was formed on a silicon wafer. The infrared absorption spectrum of this SiO ₂ film was measured in the same manner using the same apparatus as in Example 1. The infrared absorption spectrum of Comparative Example 2 is shown in FIG. In Comparative Example 2, the ratio P2 / P1 was 1.42.
Further, a gas barrier film was produced using the same PEN film as in Example 2, and the water vapor transmission rate of the gas barrier film of Comparative Example 2 was measured in the same manner using the same apparatus as in Example 2. As a result, it was 1.5 g / (m ² · day).

As described above, in Examples 1 and 2 where the gas barrier film satisfies 0 ≦ P2 / P1 ≦ 1 with respect to the ratio P2 / P1, even if the composition of the gas barrier film is different from that of SiO and SiO ₂ , Comparative Examples 1 and 2 are used. Compared to the above, it was possible to obtain excellent gas barrier performance with a water vapor permeability one order of magnitude smaller.

DESCRIPTION OF SYMBOLS 10 Film-forming apparatus 12 Supply chamber 14 Film-forming chamber 16 Wind-up chamber 20 Substrate roll 21, 24a, 24b, 25, 27, 28a, 28b, 31a, 31b Guide roller 26 Drum 30 Wind-up roll 32 Vacuum exhaust part 36 Control part DESCRIPTION OF SYMBOLS 40 Film-forming part 42,52 Heating container 44,54 Heater 46 1st temperature control part 50 Vapor deposition part 56 2nd temperature control part 59 Mask 100,100a Gas barrier film D Conveyance direction omega Rotation direction Z Substrate

Claims (7)

A gas barrier film mainly composed of silicon oxide is a gas barrier film formed on at least one surface of a substrate,
In the infrared absorption spectrum, the gas barrier film has a peak intensity of 800 to 820 cm ⁻¹ as P1, a peak intensity of 860 to 880 cm ⁻¹ as P2, and a ratio between the peak intensity P1 and the peak intensity P2 as P2. / P1, the gas barrier film is characterized in that the ratio P2 / P1 is 0 ≦ P2 / P1 ≦ 1.   The gas barrier film according to claim 1, wherein an organic film is formed between the substrate and the gas barrier film.   The gas barrier film according to claim 1 or 2, wherein the silicon oxide has an oxidation degree of 1 to 2.   The gas barrier film according to any one of claims 1 to 3, wherein the substrate is made of PET or PEN. The gas barrier film according to any one of claims 1 to 4, wherein the gas barrier film is formed by a vacuum deposition method with a moisture pressure before formation of the gas barrier film of 6 x ^10-4 Pa or less . The gas barrier film according to claim 5, wherein SiO or SiO ₂ is used as a film forming material in the vacuum deposition method.   The gas barrier film according to claim 1, wherein the gas barrier film has a thickness of 10 to 150 nm.

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