JP2005131860A - Laminated transparent gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To economically provide a laminated transparent gas barrier film excellent in gas barrier properties, especially steam barrier properties and sufficiently high in the lamination strength with a base material film even when laminated to another film. <P>SOLUTION: The laminated transparent gas barrier film is a film wherein an anchor layer and an inorganic barrier layer with a thickness of 5-30 nm are provided at least on one side of a plastic base material and the anchor layer comprises a metal oxide while the inorganic barrier layer comprises Al, Si, oxygen and nitrogen and is characterized in that the weight ratio of the Al atom to the Si atom is 15:85-40:60, the molar ratio of nitrogen to oxygen is 10-40% and the sum total mole number of the oxygen and nitrogen atoms to 100g of a pure metal component satisfies a specific formula. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a film having excellent gas barrier properties and high laminate strength when laminated with other films, for food packaging such as snack foods, rice confectionery, dry articles, cereals, etc. The present invention relates to a barrier film suitable for a material packaging, a protective film for solar cells and the like.

  As a gas barrier packaging material and package, a laminate of various plastics is used. For example, an OPP (stretched polypropylene) film and a PE (polyethylene) film, or a PET (polyester) film and a CPP (unstretched polypropylene) film laminated. Also, various packagings such as bags, cups, trays, etc., using packaging materials in which aluminum is vapor-deposited on PET film or laminated with PE or CPP film coated with vinylidene chloride or ethylene vinyl alcohol copolymer. Made and used. Recently, products using thin films such as silicon oxide and aluminum oxide as barrier films have also been proposed.

  Such conventional packaging materials and packages have the following problems. Aluminum foil or aluminum vapor deposition is excellent in gas barrier properties but is opaque and has a drawback that the contents during packaging cannot be seen. Further, when aluminum is included in the dry food packaging material and a part of the package, there is a problem that the plastic film cannot be collected and reused (recycled).

  A product containing vinylidene chloride or ethylene vinyl alcohol copolymer in a part of the structure of the dry food packaging material and the package has insufficient gas barrier properties such as water vapor and oxygen, and the storage period of the contents is short. In addition, vinylidene chloride is easily pyrolyzed and difficult to recycle, and there are concerns about the impact on the global environment such as generation of chlorine gas during incineration. In addition, although ethylene vinyl alcohol is excellent in gas barrier properties during drying, the oxygen barrier property is significantly lowered under high humidity, and the storage period is shortened. Moreover, the gas barrier film of transparent vapor deposition does not have high adhesiveness to the base material, and often causes problems such as peeling when laminated with other materials.

The thing which plasma-processed to the base film surface and improved the adhesiveness of an inorganic vapor deposition layer and a base film is proposed (for example, refer patent document 1).
JP 2001-322201 A

  However, this method is not sure of the effect of improving the laminar strength at the time of watering when the inorganic oxide is particularly weak.

On the other hand, it has been proposed to provide a metal layer on a base film to improve the laminar strength (for example, see Patent Document 2).
JP 2002-200700 A

  However, since this method is premised on metal vapor deposition, there is a concern that the transparency is lowered and the transparency characteristic of the inorganic vapor deposition film is remarkably lowered.

Moreover, an aluminum oxide thin film is provided on a plastic film, and a highly gas barrier film has been proposed (see, for example, Patent Document 3).
Japanese Patent Laid-Open No. 2001-6442

  However, although this method has a high barrier property against oxygen, it does not have a high barrier property against water vapor, and there is a drawback that it does not have a sufficient water vapor barrier property depending on the contents.

In order to solve this problem, an example using aluminum oxide / aluminum nitride and silicon has also been reported (for example, see Patent Document 4).
JP 2002-361778 A

  However, although this method describes a high barrier property against oxygen, it does not describe a water vapor barrier property.

  The present invention is economical to provide a transparent barrier film that is excellent in gas barrier properties, particularly water vapor barrier properties, and has a sufficiently high lamination strength even when laminated with other films.

That is, the gas barrier film of the present invention is a film in which an anchor layer and an inorganic barrier layer having a thickness of 5 to 30 nm are provided on at least one surface of a plastic substrate, and the anchor layer is made of a metal oxide, The barrier layer is made of Al, Si, oxygen, and nitrogen, the weight ratio of Al atoms to Si atoms is in the range of 15:85 to 40:60, and the molar ratio of nitrogen to oxygen is 10 to 40%. The total number of moles of oxygen atoms and nitrogen atoms with respect to 100 g of metal content satisfies the following formula.

Qc = _Ototal * (1-n) + _Ntotal * n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) * (4/3) (1)
= (0.017n-0.016) a-2.375n + 7.119

0.9 × Qc <Q <1.0 × Qc (2)

a: Weight of Al in 100 g of metal content (15 <a <40)
n: molar ratio of N to O (0.1 <n <0.4)
Q: Actual acid / nitridation degree Qc of thin film: Complete acid / nitridation degree calculated from calculation O _total : Total amount of oxygen necessary for complete oxide (mol)
N _total : Total amount of nitrogen required for complete nitride (mol)

  In this case, it is preferable that the metal forming the anchor layer is formed of one or more of titanium, aluminum, and silicon, and the anchor layer is formed by sputtering.

  By sequentially laminating an anchor coat layer made of metal oxide and a barrier layer made of metal oxide on a plastic film substrate, a transparent barrier film with high barrier properties and high adhesive strength can be obtained. I can do it.

  A film as a substrate is made of an organic material, hardly reacts chemically with the inorganic barrier layer, and it is difficult to obtain adhesive properties such as a laminate strength. However, the sputtering method has higher energy of particles to be deposited than the vapor deposition method, and migration is sufficiently performed on the substrate, so that high adhesion can be obtained. However, if all layers are made by sputtering, the film deposition speed is slow and the film speed needs to be very slow to obtain the film thickness necessary to provide barrier properties. Problems arise. On the other hand, the inorganic layer formed by sputtering and the second inorganic layer formed by vapor deposition or the like easily undergo chemical reaction, and high adhesion strength can be obtained with the layer formed by sputtering. In order to solve these problems, a sputter layer with high adhesion is formed as a first layer in a range that does not affect the productivity, and a film thickness sufficient to obtain barrier properties using a vapor deposition method as the second layer. The method of forming was found.

  Furthermore, silicon nitride has been studied for the purpose of improving the water vapor barrier property, but the film causes strong curl due to the strong internal stress of the thin film layer, or the thin film itself due to the strong internal stress. There was a problem of being destroyed. In addition, in order to solve the above problems, a method such as converting silicon nitride into silicon oxynitride has been used. However, the target water vapor barrier property decreases with increasing degree of oxidation, and conversely, the degree of oxidation decreases. When it decreases, the coloring becomes harder, the flexibility of the film is lowered, the film is broken by an external force, and the barrier property is lowered. Further, in the present invention, by forming a thin film of a complex acid / nitride of aluminum and silicon, there are few high water vapor barrier properties and coloring problems, and high durability against external stress, In addition, a highly adhesive barrier film can be provided.

  The plastic substrate referred to in the present invention is a film obtained by melt-extrusion of an organic polymer and stretching, cooling, and heat setting in the longitudinal direction and / or the width direction as necessary. As polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2, 6-naphthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamideimide, polyimide , Polyetherimide, polysulfone, polyphenylene sulfide, polyphenylene oxide and the like. These (organic polymers) organic polymers may be copolymerized or blended with a small amount of other organic polymers.

Furthermore, known additives such as ultraviolet absorbers, antistatic agents, plasticizers, lubricants, colorants and the like may be added to the organic polymer, and the transparency thereof is not particularly limited. When used as a transparent gas barrier film, a film having a transmittance of 50% or more is preferable.
The plastic substrate of the present invention may be subjected to corona discharge treatment, glow discharge treatment, or other surface roughening treatment prior to laminating the thin film layer as long as the object of the present invention is not impaired. Moreover, anchor coating treatment, printing, and decoration may be applied. The plastic substrate of the present invention preferably has a thickness in the range of 5 to 500 μm, more preferably in the range of 8 to 300 μm.

  The anchor layer in the present invention is considered to be composed of oxides of Al, Si, and Ti, and these ratios vary depending on the production conditions. In a state close to a metal, that is, when the degree of oxidation is extremely low, a laminar strength can be obtained. However, in order to obtain a sufficient effect, it is necessary to increase the film thickness, and the film is colored, which is not preferable. The degree of oxidation is preferably as high as possible, preferably 80% or more of the amount of oxygen necessary for complete oxidation, more preferably 90% or more. On the other hand, if the thickness of the anchor layer is thin, the effect of improvement cannot be expected. Conversely, if the thickness is too large, the effect on the laminar strength increases. However, from the viewpoint of flexibility, 1 to 8 nm is preferable, and 2 is more preferable. ~ 5 nm.

A sputtering method is used to create such an anchor layer. Among the sputtering methods, the DC magnetron sputtering method is preferable in consideration of the continuous formation with the barrier layer. More preferably, reactive sputtering using a metal as a target and performing sputtering while introducing oxygen is preferable. In order to stabilize the discharge state, the pressure is preferably between 1.3 × 10 ⁻² Pa and 1.3 Pa. In order to keep the pressure constant, it is preferable to introduce an inert gas such as Ar in addition to oxygen.

The barrier layer in the present invention contains Al, Si, O, and N as elements, and the ratio thereof varies depending on the production conditions. This component may contain a trace amount (up to 3% with respect to all components) of other components within a range where the characteristics are not impaired. The thickness of the thin film is not particularly limited, but is preferably 5 to 50 nm, more preferably 7 to 30 nm from the viewpoint of gas barrier properties and flexibility.
The nitrogen content is preferably in the range of 10 to 40% of the total of oxygen and nitrogen, and more preferably in the range of 20 to 35%. When the nitrogen content is lower than 10%, a sufficient water vapor barrier cannot be obtained, and when the nitrogen content exceeds 40%, coloring becomes intense or weak against external forces such as gelbo.

The total molar amount (ON _total ) of oxygen and nitrogen with respect to 100 g of pure metal content is calculated as follows.
1) Pure metal content When the weight of metallic aluminum in 100 g is ag, the molar amounts of Al and Si are Al _mol = a / 26.98.
Si _mol = (100−a) /28.09
It is represented by
2) The amount of oxygen required for Al ₂ O ₃ is (a / 26.98) × 1.5
The amount of oxygen required for SiO ₂ is ((100−a) /28.09) × 2
It becomes.
Therefore, the total amount of oxygen required for the complete oxide is
O _total = (a / 26.98) × 1.5 + ((100−a) /28.09) × 2
3) Since the nitride of Al is represented by AlN and the nitride of Si is represented by Si ₃ N ₄ , the amount of nitrogen necessary for AlN is a / 26.98
The amount of nitrogen required for Si ₃ N ₄ is ((100−a) /28.09) × (4/3)
Therefore, the total amount of nitrogen required for complete nitride is
N _total = a / 26.98 + (100−a) /28.09) × (4/3)
4) Here, when the molar amount of nitrogen with respect to oxygen is n, the total molar amount of oxygen and nitrogen with respect to 100 g of pure metal is ON _total = Qc
= O _total × (1-n) + N _total × n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) × (4/3)
= (0.017n-0.016) a-2.375n + 7.119

  The barrier layer of the present invention uses a metal aluminum or metal silicon as a raw material, and introduces oxygen and nitrogen in the aforementioned proportions to produce an inorganic thin film. In this case, the ratio of aluminum to silicon in the inorganic thin film is preferably 15:85 to 40:60. When the aluminum ratio is low, sufficient barrier properties cannot be obtained. Conversely, when the aluminum ratio is high, high initial barrier properties can be obtained, but the film is easily broken by external stress such as gelbo.

For the production of such an acid / nitride thin film, a PVD method (physical vapor deposition method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method is appropriately used. For example, in the vacuum deposition method, it is preferable to use a mixture of Al ₂ O ₃ , Al, SiO, SiO ₂ , SiO, or the like as an evaporation material source from the viewpoint of material handling and safety.
Further, the size of each particle needs to be an appropriate size so that the pressure during vapor deposition does not change. If the particle size is too large, it takes time to evaporate after heat is applied, and the pressure fluctuation increases. If the particle size is too small, bumping occurs, causing splash.
As a heating method, resistance heating, high frequency induction heating, electron beam heating, laser heating, or the like can be used. Further, as the reactive gas, oxygen, nitrogen, water vapor or the like may be introduced, or reactive vapor deposition using means such as ozone addition or ion assist may be used.
The emission current is preferably between 0.3 A and 1.0 A, more preferably between 0.5 and 0.8 A. When the emission current is less than 0.3 A, a sufficient evaporation rate cannot be obtained, and productivity is lowered. Further, if the emission current becomes too large, the amount of evaporation becomes too large, the pressure rises and the decomposition of alumina becomes large, and it becomes difficult to control the pressure.

  The oxygen / nitrogen concentrations in the present invention are oxygen / nitrogen concentrations contained in a thin film measured by using an X-ray photoelectron spectroscopy (hereinafter referred to as ESCA) or an Auger electron microscope. In the above method, the amount of aluminum, silicon and titanium can be measured at the same time, and the ratio of the five can be measured. In addition, by etching the thin film using argon or the like, variation in composition in the thickness direction of the thin film can be measured.

  Next, an Example is given and this invention is demonstrated.

Next, methods for measuring oxygen transmission rate and water vapor transmission rate, bending fatigue resistance, and laminar strength testing methods are shown.
1) Measuring method of oxygen permeability (OTR) The oxygen permeability of the prepared gas barrier film was measured using an oxygen permeability measuring device (OX-TRAN100 manufactured by Modern Controls).
2) Measuring method of water vapor transmission rate (WVTR) The prepared sample was measured at 40 ° C., 100% R.D. H. The measurement was performed using a measuring device (PARMATRAN-W) manufactured by MOCON, USA.
3) Test method for bending fatigue resistance (hereinafter referred to as gelbo characteristics) The bending fatigue resistance was evaluated using a so-called gelboflex tester (manufactured by Rigaku Corporation). The conditions are (MIL-B131H), a 11.2 inch × 8 inch sample piece is cylindrical with a diameter of 3 (1/2) inch, both ends are held, an initial gripping interval is 7 inches, and a stroke 3 (1/2) The reciprocating motion of this operation was performed at a speed of 40 times / min under the conditions of 20 ° C. and 65% relative humidity.
4) Measuring method of Lami strength TM590 / CAT56 manufactured by Toyo Morton Co., Ltd. was mixed at a weight ratio of 15: 2.4, applied with a bar coater to a dry coating amount of 3 g, and a polyethylene film manufactured by Toyobo Co., Ltd. (L6102, 40 μm). ) Was laminated. This was cut into a width of 15 mm and a length of 100 mm, and the peel strength between the polyethylene film and the base PET film was measured.

(Example 1)
In a continuous vapor deposition apparatus as shown in FIG. 1, a magnetron sputtering target 2 is arranged toward a cooling roll 1. A titanium plate having a purity of 99.5% was used as the target. A partition plate for preventing the outflow of gas was provided around the target so that the pressure in the vicinity of the target did not affect the deposition chamber. Sputtering was performed on a 12 μm thick PET film (Toyobo Co., Ltd .: E5100). The sputtering pressure was set to 5.3 × 10 ⁻¹ Pa by introducing 15 SCCM of O ₂ . Reactive sputtering was performed by introducing oxygen. The completed thin film was titanium oxide. The input power was 4.7 W / cm ² . The running speed of the film was 130 m / min, and the film thickness was 3 nm. After providing a thin film of TiO _{2 on} the film, an inorganic vapor deposition film was continuously processed.

The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -Gas barrier layer of silicon acid / nitride was formed. The mixing ratio of aluminum and SiO ₂ was set to a weight ratio of 25:75. The output of the electron beam was 0.5 A, the film feed rate was 100 m / min, and a 15 nm thick film was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure at the time of vapor deposition was adjusted to 3.3 × 10 ⁻² Pa by introducing nitrogen gas and oxygen gas. The oxygen partial pressure at this time was 1.3 × 10 ⁻³ Pa, and the nitrogen partial pressure was 2.5 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Example 2)
The target is a mixture of aluminum and silicon (weight ratio 40:60), the input power is 5.2 W / cm ^2, and reactive sputtering is performed while introducing ₂₀ SCCM of O ₂ to form a mixed oxide thin film of aluminum and silicon. did. The thin film was 3 nm. The vapor deposition film produced the film on the same conditions as Example 1. FIG.

(Example 3)
The target was aluminum, the input power was 3.3 W / cm ^2, and reactive sputtering was performed while introducing 15 SCCM of oxygen to form an aluminum oxide thin film. The film thickness was 3 nm. The vapor deposition film produced the film on the same conditions as Example 1. FIG.

Example 4
A titanium plate having a purity of 99.5% was used as the target. A partition plate for preventing the outflow of gas was provided around the target so that the pressure in the vicinity of the target did not affect the deposition chamber. Sputtering was performed on a 12 μm thick PET film (Toyobo Co., Ltd .: E5100). The sputtering pressure was set to 5.3 × 10 ⁻¹ Pa by introducing 15 SCCM of O ₂ . Reactive sputtering was performed by introducing oxygen. The completed thin film was titanium oxide. The input power was 4.7 W / cm ² . The running speed of the film was 130 m / min, and the film thickness was 3 nm. After providing a thin film of TiO _{2 on} the film, an inorganic vapor deposition film was continuously processed.

The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 40:60 by weight. The output of the electron beam was 0.5 A, the film feed rate was 100 m / min, and a film having a thickness of 150 nm was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure at the time of vapor deposition was adjusted to 3.3 × 10 ⁻² Pa by introducing nitrogen gas and oxygen gas. At this time, the oxygen partial pressure was 2.6 × 10 ⁻³ Pa, and the nitrogen partial pressure was 2.3 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 1)
Without forming an anchor coat, a deposited film was directly formed on PET. The deposited film was created under the same conditions as in Example 1.

(Comparative Example 2)
An anchor layer was created under the same conditions as in Example 1. The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 10:90 by weight. The output of the electron beam was 0.45 A, the film feed rate was 100 m / min, and a 15 nm thick film was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure at the time of vapor deposition was adjusted to 3.3 × 10 ⁻² Pa by introducing nitrogen gas and oxygen gas. The oxygen partial pressure at this time was 1.3 × 10 ⁻² Pa, and the nitrogen partial pressure was 2.5 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 3)
An anchor layer was created under the same conditions as in Example 1. The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 90:10 by weight. The output of the electron beam was 0.55 A, the film feed rate was 100 m / min, and a 15 nm thick film was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure during deposition was adjusted to 3.3 × 10 ⁻² Pa by introducing nitrogen gas. The oxygen partial pressure at this time was 1.1 × 10 ⁻² Pa, and the nitrogen partial pressure was 1.3 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 4)
In a continuous vapor deposition apparatus as shown in FIG. 1, a magnetron sputtering target 2 is arranged toward a cooling roll 1. A titanium plate having a purity of 99.5% was used as the target. A partition plate for preventing the outflow of gas was provided around the target so that the pressure in the vicinity of the target did not affect the deposition chamber. Sputtering was performed on a 12 μm thick PET film (Toyobo Co., Ltd .: E5100). The sputtering pressure was set to 5.3 × 10 ⁻¹ Pa by introducing 10 SCCM of Ar. The input power was 4.7 W / cm ² . After providing a Ti thin film on the film, an inorganic vapor deposition film was continuously processed. The deposited film was created under the same conditions as in Example 1.

(Comparative Example 5)
In a continuous vapor deposition apparatus as shown in FIG. 1, a magnetron sputtering target 2 is arranged toward a cooling roll 1. A titanium plate having a purity of 99.5% was used as the target. A partition plate for preventing the outflow of gas was provided around the target so that the pressure in the vicinity of the target did not affect the deposition chamber. Sputtering was performed on a 12 μm thick PET film (Toyobo Co., Ltd .: E5100). The sputtering pressure was 5.3 × 10 ⁻¹ Pa by introducing O ₂ with 10 SCCM. The input power was 5.5 W / cm ² . A 9 nm thin film was prepared at a film feed rate of 75 m / min. After providing a Ti thin film on the film, an inorganic vapor deposition film was continuously processed.

The inorganic vapor deposition film is prepared by electron beam vapor deposition using aluminum particles having a particle size of about 3 mm to 5 mm (purity 99.5%) and SiO ₂ of about 3 mm to 5 mm as a vapor deposition source. -A gas barrier layer of silicon oxidation / nitridation was formed. The mixing ratio of aluminum and SiO ₂ was 25:75 by weight. The output of the electron beam was 0.375 A, the film feed rate was 75 m / min, and a 15 nm thick film was formed. The vacuum layer contains an unwinding part, a coating part, and a winding part, and can be continuously deposited on the film. The pressure at the time of vapor deposition was adjusted to 3.3 × 10 ⁻² Pa by introducing nitrogen gas and oxygen gas. The oxygen partial pressure at this time was 1.3 × 10 ⁻² Pa, and the nitrogen partial pressure was 2.5 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

(Comparative Example 6)
In a continuous vapor deposition apparatus as shown in FIG. 1, a magnetron sputtering target 2 is arranged toward a cooling roll 1. A titanium plate having a purity of 99.5% was used as the target. A partition plate for preventing the outflow of gas was provided around the target so that the pressure in the vicinity of the target did not affect the deposition chamber. Sputtering was performed on a 12 μm thick PET film (Toyobo Co., Ltd .: E5100). The sputtering pressure was 5.3 × 10 ⁻¹ Pa by introducing O ₂ with 10 SCCM. The input power was 5.5 W / cm ² . A 9 nm thin film was prepared at a film feed rate of 75 m / min. After providing a Ti thin film on the film, an inorganic vapor deposition film was continuously processed.

The inorganic vapor-deposited film is produced by electron beam vapor deposition using, as a vapor deposition source, particulate SiO ₂ (purity 99.9%) and Al ₂ O ₃ (purity 99.9%) of about 3 to 5 mm. A mixed gas barrier layer of aluminum oxide and silicon dioxide was formed on the PET film subjected to anchor coating. The evaporation material was divided into two parts without mixing. An electron gun (hereinafter referred to as an EB gun) was used as a heating source, and two types of raw materials were heated in a time division manner. At that time, the emission current of the EB gun was set to 1.2 A, and the heating ratio of SiO ₂ to Al ₂ O ₃ was set to 1: 2. The film feed rate was 130 m / min, and a 20 nm thick film was produced. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC. In order to measure the oxygen concentration of the thin film, a portion of the obtained gas barrier film was cut out and the ratio of oxygen concentration and Al, Si, O was measured using ESCA. The weight ratio of Al to Si was 40:60.

[Create laminate film]
A polyurethane-based adhesive (manufactured by Toyo Morton Co., Ltd., main agent / curing agent TM-590 / CAT56) was applied to the deposited surfaces of the obtained Examples 1 to 4 and Comparative Examples 1 to 6 by heat treatment at 80 ° C. After that, a low density polyethylene film (L6102 thickness 40 μm, manufactured by Toyobo Co., Ltd.) was dry laminated on a metal roll heated to 80 ° C. at a nip pressure of 490 kPa to obtain a laminate film. About the obtained laminate film, the oxygen permeation amount and the water vapor permeation amount before and after the gelbo were prepared.

  Table 1 shows the measurement results of Examples 1 to 4 and Comparative Examples 1 to 6.

  The present invention relates to a protective layer for electronic materials such as foods that are excellent in gas barrier properties, particularly water vapor barrier properties, dislike moisture, pharmaceuticals that require high water vapor barrier properties, packaging materials for electronic materials, and organic EL and solar cells. .

It is a schematic diagram of a continuous vapor deposition apparatus.

Explanation of symbols

1: Cooling roll 2: Magnetron sputtering device 3: Deposition crucible 4: Electron gun 5: Unwinding roll 6: Winding roll

Claims (2)

A film in which an anchor layer and an inorganic barrier layer having a thickness of 5 to 30 nm are provided on at least one surface of a plastic substrate, wherein the anchor layer is made of a metal oxide, and the inorganic barrier layer includes Al, Si, and oxygen Made of nitrogen, the weight ratio of Al atom to Si atom is in the range of 15:85 to 40:60, the molar ratio of nitrogen to oxygen is 10 to 40%, and the oxygen atom and nitrogen atom with respect to 100 g of pure metal content The total number of moles of the gas barrier film satisfies the following formula.

Qc = _Ototal * (1-n) + _Ntotal * n
= (0.056a + (3.559-0.036a) * 2) (1-n)
+ (0.037a + 3.559-0.036a) * (4/3) (1)
= (0.017n-0.016) a-2.375n + 7.119

0.9 × Qc <Q <1.0 × Qc (2)

a: Weight of Al in 100 g of metal content (15 <a <40)
n: molar ratio of N to O (0.1 <n <0.4)
Q: Actual acid / nitridation degree Qc of thin film: Complete acid / nitridation degree calculated from calculation O _total : Total amount of oxygen necessary for complete oxide (mol)
N _total : Total amount of nitrogen required for complete nitride (mol)
  2. The gas barrier film according to claim 1, wherein the metal forming the anchor layer is formed of one or more of titanium, aluminum and silicon, and the anchor layer is formed by sputtering. Gas barrier film characterized by

Images