JP2002192646A - Gas-barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-barrier film having excellent gas-barrier properties while keeping a prescribed thickness. SOLUTION: In the gas-barrier film having a silicon oxide film formed by a plasma CVD method at least on one side of a base material, the silicon oxide film comprises 170-200 oxygen atoms and 30 or below carbon atoms per 100 silicon atoms and has IR absorption based on Si-O-Si stretching vibration in a range of 1,055-1,065 cm-1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film mainly used as a packaging material for foods and pharmaceuticals and a packaging material for electronic devices and the like.
The present invention relates to a gas barrier film having a silicon oxide film having excellent gas barrier properties.

[0002]

2. Description of the Related Art Gas barrier films are mainly used as packaging materials for foods, pharmaceuticals, etc. in order to prevent the influence of oxygen, water vapor, etc., which may cause the quality of the contents to change, or to be used for liquid crystal display panels and EL displays. Elements formed on panels and the like are used as package materials for electronic devices and the like in order to avoid performance degradation due to contact with oxygen or water vapor. In recent years, a gas barrier film is sometimes used for the purpose of giving flexibility and impact resistance to a portion where glass or the like is conventionally used.

[0003] Such a gas barrier film generally has a structure in which a gas barrier layer is formed on one or both sides of a plastic film as a base material. The gas barrier film is formed by CVD, PVD
It is formed by various methods such as a sputtering method and a sputtering method. Regardless of which method is used, the conventional gas barrier film has an oxygen transmission rate (OTR) of about ² cc / m ² / day, It has a water vapor transmission rate (WVTR) of only about ² g / m ² / day, and is still insufficient when used for applications requiring higher gas barrier properties.

As a method of dry-forming a film having gas barrier properties on a polymer resin substrate, a silicon oxide film (silica film) or an aluminum oxide film (alumina film) is formed by a dry film-forming method such as a plasma CVD method. Are known. For example, JP-A-8-176326, JP-A-11-176
No. 309815 and JP-A-2000-6301. In particular, the plasma CVD method has an advantage that a silicon oxide film or an aluminum oxide film having excellent gas barrier properties and flexibility can be formed without thermally damaging the polymer resin substrate.

In general, the gas barrier properties of a gas barrier film improve as the thickness of the vapor deposition barrier layer increases. However, in recent years, in the Society of Vacuum Coaters, J.
T. Felts et al. (34th Annual Technical Conference Proceed
ings (1991), p. 99-104) and JEKlemberg-Sapieha et al. (36t
h Annual Technical Conference Proceedings (1993), p.
445-449) point out that as the film thickness increases and the internal stress of the film is alleviated, cracks are generated in the barrier film, and the gas permeability is rather increased.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its main object to provide a gas barrier film having extremely excellent gas barrier properties while maintaining a predetermined thickness. And

[0007]

According to a first aspect of the present invention, there is provided a semiconductor device having a silicon oxide film formed on one or both sides of a substrate by a plasma CVD method. A gas barrier film, wherein the silicon oxide film has a number of O atoms of 170 with respect to a number of Si atoms of 100.
It has become the 200 and C atoms of 30 or less component ratio, further Si-O between 1055～1065Cm ^-1
-Provide a gas barrier film characterized by having IR absorption based on Si stretching vibration.

According to the present invention, a gas barrier film having extremely excellent gas barrier properties can be obtained by controlling the characteristics of the silicon oxide film acting as a gas barrier film, which comprises the component ratio and IR absorption, within the above ranges. Can be. A silicon oxide film having such characteristics is a dense, low-impurity SiO ₂ -like film.

According to the first aspect of the present invention, as described in the second aspect, in the gas barrier film, the silicon oxide film has a refractive index of 1.45 to 1.4.
8 is preferable. This is because the gas barrier property can be further improved by controlling the refractive index of the silicon oxide film acting as the gas barrier film within the above range.

[0010] In the present invention, there is provided a method as set forth in claim 3, wherein: a base material;
Wherein the distance between grains formed on the surface of the vapor-deposited film is 5 to 40 nm.

According to the present invention, by controlling the distance between the grains formed on the surface of the vapor deposition film acting as a gas barrier film to be within the above range, the gas permeable area can be reduced. A gas barrier film having extremely excellent gas barrier properties can be obtained.

In the invention described in claim 3, it is preferable that the deposited film is a silicon oxide film, as described in claim 4.

[0013] Furthermore, the present invention relates to claim 5,
A gas barrier film having a substrate and a silicon oxide film formed on both surfaces or one surface of the substrate, wherein the silicon oxide film has an E ′ center observed by electron spin resonance (ESR) measurement. The present invention provides a gas barrier film having:

The E 'center, that is, the silicon oxide film having silicon atoms having unpaired electrons has a densely distorted structure, so that a gas barrier film having extremely excellent gas barrier properties can be obtained.

According to the fifth aspect of the present invention, as described in the sixth aspect, the density of the E ′ center is 5
It is preferably at least × 10 ¹⁵ spins / cm ³ .

The density of the E 'center is 5 × 10 ¹⁵ spin
This is because the silicon oxide film having a thickness of s / cm ³ or more can be said to have a structure in which the structure of the film is surely distorted, and the gas barrier film having this structure has extremely excellent performance.

Further, the present invention is a gas barrier film according to claim 7, comprising a base material and a silicon oxide film formed on both sides or one side of the base material, wherein the silicon oxide film is 2341 ± 4 cm ^The present invention provides a gas barrier film characterized by having an IR absorption peak based on stretching vibration of CO molecules at ^-1 .

According to the present invention, a gas barrier film having extremely excellent gas barrier properties can be obtained by controlling the characteristics comprising IR absorption of the silicon oxide film acting as a gas barrier film as described above.

In the invention according to any one of the first to seventh aspects, as described in the eighth aspect, the oxygen permeability is 0.5 cc / m ² / day or less, It is preferable that the transmittance is 0.5 g / m ² / day or less.

By setting the oxygen permeability and the water vapor permeability within the above ranges, almost no oxygen and water vapor which cause a change in the quality of the contents are permeated, so that they are preferably used for applications requiring high gas barrier properties. Because you can do it.

In the invention described in any one of the first to eighth aspects, as described in the ninth aspect, the thickness of the deposited film is in the range of 5 to 300 nm. Is preferred.

According to the present invention, even when an extremely thin deposited film having a thickness of 5 to 300 nm is formed, excellent gas barrier properties can be exhibited, and the deposited film can be prevented from cracking. is there. Further, a gas barrier film having a vapor-deposited film having a thickness in the above-mentioned range is preferable in terms of productivity because it does not impair transparency or appearance and can suppress an increase in curling of the film.

Further, in the present invention, a silicon oxide film is formed on a substrate by a plasma CVD method in a reaction chamber using a gas containing at least an organic silicon compound gas and a gas containing oxygen atoms as a source gas. Wherein the component of the organic silicon compound gas is a compound having no carbon-silicon bond in the molecule, and the temperature of the substrate at the start of film formation is-
The silicon oxide film is formed within the range of 20 ° C. to 100 ° C. and the flow rate ratio of the organic silicon compound gas to the gas containing oxygen atoms is set to 3 to 50 when the organic silicon compound gas is set to 1. The present invention provides a method for producing a gas barrier film, which comprises forming a film and then performing a heat treatment in a range of 50 ° C to 200 ° C.

By employing a manufacturing method in which the silicon oxide film thus obtained is further subjected to a heat treatment, a gas barrier film having better gas barrier properties can be obtained.

Further, in the present invention, as described in claim 11, a heat-sealing resin is provided on at least one surface of the gas barrier film according to any one of claims 1 to 9. A laminated material provided with a layer is provided. When such a laminated material is used, as described in claim 12, a packaging container can be obtained by heat-sealing the heat-sealable resin layer of the laminated material to form a bag or a box. Since the packaging container has excellent gas barrier properties, it can be suitably used as a packaging material for foods, medicines, and electronic devices.

In the present invention, as described in claim 13, a conductive layer is provided on at least one surface of the gas barrier film according to any one of claims 1 to 9. A laminated material characterized by being formed is provided. By using such a laminated material, an image display medium can be obtained by forming an image display layer on the conductive layer as described in claim 14. Since the base material used as the base material of the image display medium is excellent in gas barrier properties and flexibility, the image display medium can be excellent in weather resistance and impact resistance.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The gas barrier film of the present invention will be specifically described below with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of the configuration of the gas barrier film of the present invention. As shown in FIG.
The gas barrier film 1 of the present invention includes a substrate 2 and a vapor deposition film 3 formed on both sides or one side of the substrate 2. Hereinafter, this deposited film, and the substrate, further,
The method for manufacturing the gas barrier film will be described separately.

A. Vapor Deposition Film The present invention is characterized by this vapor deposition film, and can be divided into four embodiments according to its characteristics. Hereinafter, each will be described.

1. First Embodiment The deposited film in this embodiment is preferably a plasma CV
This is a silicon oxide film formed by the D method.
Of 100 and a component ratio of 30 or less C atoms.
It is characterized in that there is IR absorption based on the Si—O—Si stretching vibration between 55 and 1065 cm ⁻¹ . That is, the feature of the present invention is that, by controlling each characteristic comprising the component ratio of the silicon oxide film 3 acting as a gas barrier film and IR absorption within the above range, extremely excellent gas barrier properties are exhibited. It is in.

The silicon oxide film has a component ratio of 170 to 200 O atoms and 30 or less C atoms with respect to 100 Si atoms, and has a S content of 1055 to 1065 cm ^-1.
It is formed so that there is IR absorption based on i-O-Si stretching vibration. Further, at this time, it is more preferable to form it so as to have a refractive index of 1.45 to 1.48. The gas barrier film 1 including the silicon oxide film 3 having such characteristics exhibits extremely excellent gas barrier properties.

In order to make the respective component ratios of Si, O and C equal to 170 to 200 O atoms and 30 or less C atoms with respect to 100 Si atoms, the flow ratio of the organic silicon compound gas to the oxygen gas and the The power can be controlled within the above range by adjusting the input power per unit flow rate of the silicon compound gas. In particular, it is preferable to control so as to suppress the mixing of C. For example, by adjusting the flow ratio of (oxygen gas / organic silicon compound gas) in the range of about 3 to 50, it is possible to suppress the incorporation of C into a SiO ₂ -like film, or to reduce the per unit flow rate of the organic silicon compound gas. , The breaking of Si—C bonds can be facilitated and the incorporation of C into the film can be suppressed. In addition,
The upper limit of the flow ratio is defined for convenience, and there is no particular problem if it exceeds 50. Since a silicon oxide film having a component composition in this range has few Si—C bonds, it becomes a SiO ₂ -like homogeneous film, and exhibits extremely excellent gas barrier properties. The component ratio may be any device that can quantitatively measure each component of Si, O, and C. A typical measuring device is ESCA (Electron spectroscopy for chemic).
alanalysis) and RBS (Rutherford back scatterin)
g), assessed by results measured by Auger electron spectroscopy.

When the O component ratio is less than 170,
(Oxygen gas / organic silicon compound gas) The flow rate ratio is small (when the oxygen gas flow rate is relatively small) or when the input power per unit flow rate of the organic silicon compound gas is small. Is increased. As a result, the film has many Si—C bonds in the film, and is not a SiO ₂ -like homogeneous film, so that the oxygen permeability and the water vapor permeability increase, and sufficient gas barrier properties cannot be exhibited. Note that the number of O atoms is stoichiometrically hard to exceed 200. When the component ratio of C exceeds 30, the same condition as when the component ratio of O is less than 170, that is, when the flow ratio of (oxygen gas / organic silicon compound gas) is small (the oxygen gas flow rate is relatively low) This is often seen when the input power per unit flow rate of the organosilicon compound gas is small, and the Si—C bond remains in the film as it is. As a result, the film is no longer a SiO ₂ -like homogeneous film, and the oxygen transmission rate and the water vapor transmission rate increase, so that sufficient gas barrier properties cannot be exhibited. On the other hand, although the lower limit of the component ratio of C is not particularly defined, it can be defined as 10 as the lower limit in the actual film forming process. In addition, the component ratio of C is 1
Although it is not easy to make it less than 0, C
May be less than 10, and a SiO ₂ -like homogeneous film is obtained.

In the IR measurement, 1055 to 1065c
To an absorption based on the stretching vibration of SiO-Si between m ^-1, the flow rate of only to the SiO ₂ -like uniform film, the organic silicon compound gas and oxygen gas can a silicon oxide film By controlling the input power per unit flow rate of the organic silicon compound gas or the like, the control can be performed within the above range. For example, the flow rate ratio of (oxygen gas / organic silicon compound gas) is adjusted in the range of about 3 to 50, or the input power per unit flow rate of the organic silicon compound gas is increased to easily break the Si—C bond. By doing, Si
An O ₂ -like film can be obtained. Note that the upper limit of the flow rate ratio is defined for convenience, and there is no particular problem if it exceeds 50. The silicon oxide film exhibiting such IR absorption is S
Since it has a Si—O bond unique to an iO ₂ -like homogeneous film, it exhibits extremely excellent gas barrier properties. IR absorption is measured and evaluated with an infrared spectrophotometer for IR measurement. Preferably, the infrared spectrophotometer has an ATR (multiple reflection)
Attach a measuring device and measure the infrared absorption spectrum.
At this time, it is preferable to use a germanium crystal for the prism and measure at an incident angle of 45 degrees.

If there is no IR absorption in this range, (oxygen
When the flow ratio of gas / organic silicon compound gas is small (acid
(When the gas flow rate is relatively small) or organic silicon compound gas
Often when the input power per unit flow of
As a result, the component ratio of C increases. The result
As a result, the film has a Si-C bond,
_Two Relatively few Si-O bonds peculiar to like homogeneous film
That is, no IR absorption appears within the above range. So get it
The silicon oxide film has high oxygen permeability and water vapor permeability.
Therefore, sufficient gas barrier properties cannot be exhibited.

The silicon oxide film has a refractive index of 1.45 to 1.48.
In order to achieve this, the flow rate can be controlled within the above range by adjusting the flow ratio between the organic silicon compound gas and the oxygen gas, the amount of input power per unit flow rate of the organic silicon compound gas, and the like. For example, it can be controlled by adjusting the flow ratio of (oxygen gas / organic silicon compound gas) in the range of about 3 to 50. Note that the upper limit of the flow rate ratio is defined for convenience, and there is no particular problem if it exceeds 50. A silicon oxide film having a refractive index in this range is dense and has few impurities.
It becomes an iO ₂ -like film and exhibits extremely excellent gas barrier properties. Such a refractive index is obtained by measuring the transmittance and the reflectance measured by an optical spectroscope, and evaluating the refractive index at 633 nm using an optical interference method.

When the refractive index is less than 1.45, the flow rate ratio between the organic silicon compound gas and the oxygen gas is out of the above range, or the input power per unit flow rate of the organic silicon compound gas is small and low. This is often seen when a silicon oxide film with a low density is obtained, and the formed silicon oxide film becomes sparse, and the oxygen transmission rate and the water vapor transmission rate increase, so that sufficient gas barrier properties cannot be exhibited. On the other hand, when the refractive index exceeds 1.48, it is often seen when the flow rate ratio of the organic silicon compound gas to the oxygen gas is out of the above range or when impurities such as C (carbon) are mixed. Since the formed silicon oxide film becomes sparse, the oxygen transmission rate and the water vapor transmission rate increase, and sufficient gas barrier properties cannot be exhibited.

The silicon oxide film having each of the above-described characteristics is
A gas barrier film formed with a small thickness of about 300 nm can exhibit excellent gas barrier properties and hardly cause cracks in a silicon oxide film. When the thickness of the silicon oxide film is less than 5 nm, the silicon oxide film may not be able to cover the entire surface of the base material, and the gas barrier property cannot be improved. On the other hand, when the thickness of the silicon oxide film is 300
If the thickness exceeds nm, cracks are easily formed, transparency and appearance are reduced, curling of the film is increased, and mass production is difficult, productivity is reduced, and costs are increased. Is more likely to occur.

When the gas barrier film of the present invention is used for applications requiring flexibility, such as a packaging material, the thickness of the silicon oxide film to be formed should be 5 to 5 in consideration of the mechanical properties and application of the formed silicon oxide film. More preferably, it is 30 nm. By setting the thickness of the silicon oxide film to 5 to 30 nm, flexibility as a soft packaging material can be provided, and generation of cracks when the film is bent can be prevented. Further, when the gas barrier film of the present invention is used for applications that do not require relatively thin, for example, gas barrier films for film liquid crystal displays, gas barrier films for film organic EL displays, or gas barrier films for film solar cells, , Since gas barrier properties are required first, it is preferable to make the thickness larger than the above-mentioned range of 5 to 30 nm, and the thickness is set to 30 to 20 nm.
It is more preferable to set it to 0 nm in consideration of productivity and the like.

By using the gas barrier film of the present invention for the above-mentioned applications, it is possible to make the film thinner than a conventional product having the same gas barrier properties.

The silicon oxide film of the present embodiment is preferably formed on one or both surfaces of the above-mentioned base material by, but not limited to, a plasma CVD method. The plasma CVD method is a method in which a raw material gas at a constant pressure is discharged to be in a plasma state, and a chemical reaction on a substrate surface is promoted by active particles generated in the plasma to form the gas. This plasma CVD method uses a low temperature (about -10 to 10
There is an advantage that a desired material can be formed at a temperature of about 200 ° C., and the type and physical properties of the obtained film can be controlled by the type and flow rate of the raw material gas, the film forming pressure, the input power, and the like.

The silicon oxide film 3 supplies a mixed gas of an organosilicon compound gas and an oxygen gas at a predetermined flow rate into a reaction chamber of a plasma CVD apparatus, and supplies a DC power or a low-frequency to high-frequency voltage to an electrode. Is generated on the base material by generating a plasma by applying an electric power having a constant frequency of, and reacting an organic silicon compound gas with a gas containing oxygen atoms, particularly an oxygen gas in the plasma. The type of plasma CVD device used is not particularly limited,
Various types of plasma CVD devices can be used. Usually, an apparatus capable of continuously forming a silicon oxide film while using a long polymer resin film as a base material and transporting the same is preferably used.

In the present embodiment, the silicon oxide film is transparent. However, in order to use the silicon oxide film for various purposes, it is possible to arbitrarily laminate a layer having poor transparency among the base material and other laminated materials. In addition, the transparency and the degree of the gas barrier film required as a final product differ depending on various uses. For example, when the gas barrier film using the silicon oxide film of the present embodiment is used as a packaging material,
In order to protect the contents from light rays, they may be printed with colored ink or the like to provide light-shielding properties. In addition, a layer in which an additive such as an antistatic agent and a filler that deteriorates the transparency of the entire gas barrier film is kneaded may be laminated, or a non-transparent metal foil or the like may be laminated. However, when used in applications such as a gas barrier film for a film liquid crystal display, a gas barrier film for a film organic EL display, or a gas barrier film for a film solar cell, the transparency of the entire gas barrier film is required. The effect of the transparency of the silicon film is great.

2. Second Embodiment Next, a second embodiment will be described. As shown in FIG. 2 and FIG.
The distance L between the grains 3a formed on the surface of the vapor deposition film 3 is 5 to 40.
It has a feature in the area of nm.

The portion of the grain 3a is a portion having high crystallinity in the deposited film 3, and has a property that gas and water vapor are hardly permeated. Therefore, by setting the distance L between grains within the above range, a region through which a gas or the like can pass in the deposited film (a portion other than the grains) is reduced, so that the barrier property can be improved. When the distance L between the grains is in the above range, that is, 5 to 40 nm, a vapor-deposited film having good barrier properties can be obtained, and a more preferable range of the distance L between the grains is 1
0 to 30 nm.

Here, the grains 3a formed on the surface of the deposition film 3 will be described. Grain is defined by dividing a cross section of an AFM image obtained by observing the surface of a vapor-deposited film with an atomic force microscope (AFM) at a predetermined height.
A part that appears as an island when converted to a value. That is, irregularities are formed on the surface of the vapor-deposited film 3, and observation and image processing were performed using an atomic force microscope to make the irregularities easy to understand, and the processing resulted in an island shape, that is, a convex portion. It is a part.

The distance L between the grains refers to the distance from the peak of the grain (the vertex of the convex portion) to the peak of the adjacent grain. From the distance L between the grains, it is possible to know how large the grains (convex portions) exist per unit length, and also to understand the density of the grains formed on the surface of the deposited film.

The type of film that can be used as the vapor deposition film in this embodiment may be a transparent film or an opaque film, and is not particularly limited.

When the deposited film is a transparent film, the film types include aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, and the like. Zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, barium oxide, and the like can be given. In addition, an ITO film or the like can be used as the deposition film of this embodiment.

On the other hand, when the opaque film is used, examples of the film type include aluminum, silicon, and the like, and all metals can be used as the deposited film in the present embodiment.

In the present embodiment, among them, a silicon oxide film is the most preferable material from the viewpoint of easiness of production and versatility of use.

The thickness of the deposited film of this embodiment is the same as the description of the thickness of the silicon oxide film in the first embodiment, and the description is omitted here.

As a method for manufacturing the above-mentioned deposited film, it is preferable to form the film by a plasma CVD method, a PVD method (such as an ion plating method) or a sputtering method. This is because, when the gas barrier film of the present invention is manufactured by a plasma CVD method, the film has flexibility as a whole and can be used for various applications. Further, when the gas barrier film of the present invention is manufactured by a PVD method (for example, an ion plating method), since the productivity is high, the utility value of the gas barrier film of the present invention can be improved. Furthermore, the sputtering method has conventionally been suitable for forming a film having a high gas barrier property, and therefore can be suitably used in the present invention. In the present invention, among others, plasma CVD
It is preferably formed by a method.

In order to measure the inter-grain distance of the film formed by the plasma CVD method, as described later, the surface of the film is exposed with a highly crystalline grain portion using a hydrofluoric acid aqueous solution or the like. It is also possible to measure these distances using a surface shape measuring device such as AFM.

In order to manufacture the gas barrier film of the present invention, it is necessary to adjust the distance between the grains formed on the surface of the deposited film. It is preferable to make the deposited film forming material reach the surface of the base material with energy, and to increase the input power in order to form a structurally stable and dense film.

Further, when a vapor-deposited film is formed, by making the vapor-deposited molecules easily migrate on the surface of the base material, a dense and structurally stable film can be obtained. It is also preferable to increase the temperature.

3. Third Embodiment The deposited film in this embodiment is a silicon oxide film, and this embodiment is characterized in that this silicon oxide film has an E ′ center observed by electron spin resonance (ESR) measurement. It is assumed that.

First, the E 'center will be described.

The E ′ center is an unpaired electron, and the following [Formula 1] is a structural formula of an E ′ center, that is, a silicon atom having an unpaired electron.

[0060]

Embedded image

A normal silicon atom has four arms for covalent bonding to another element, and therefore, a silicon atom in a normal silicon oxide film is bonded to four adjacent oxygen atoms. However, in the E ′ center, ie, a silicon atom having an unpaired electron, three of the four arms are bonded to an oxygen atom, while the fourth arm is present as an unpaired electron, Does not form a covalent bond with an atom. For this reason,
A silicon oxide film composed of silicon atoms having an E 'center has a structure in which the film is densely distorted. Therefore,
The silicon oxide film having the E ′ center is in a state where crystals are more compact than the crystal structure of a normal silicon oxide film (since there is no single bond between a silicon atom and an oxygen atom, another silicon atom is also included in that portion. And oxygen atoms can enter), so that a gas barrier film having extremely excellent gas barrier properties can be obtained.

Here, the electron spin resonance method (ESR)
Method) The density of the E 'center observed by measurement is 5
It is preferably at least × 10 ¹⁵ spins / cm ³ .

The density of the E ′ center is 5 × 10 ¹⁵ spin
This is because the silicon oxide film having a thickness of s / cm ³ or more surely has a structure in which the film is densely distorted.

The density of the E ′ center is 1 × 10 ¹⁸
It is preferably at most spins / cm ³ . An increase in the density of the E 'center means that bonds between silicon atoms and oxygen atoms are reduced. When the above value is exceeded, it is difficult to form a film as a crystal.

Next, the electron spin resonance method (ESR method) will be described.

A substance having an unpaired electron such as a radical or a transition metal ion and exhibiting magnetism by its spin is called a paramagnetic substance, and a substance having no unpaired electron is called a diamagnetic substance. Here, the electron spin resonance method (ESR method) is an absorption spectrum method using unpaired electrons of a paramagnetic substance. The electron spin resonance method (ESR method) describes the electronic state and the environment in which it is placed. Information can be obtained.

When measuring the silicon oxide film constituting the gas barrier film of this embodiment, any of the conventionally known electron spin resonance methods can be used.
The measuring device and the like are not particularly limited.

The thickness of the silicon oxide film of this embodiment is the same as the description of the thickness of the silicon oxide film of the first embodiment, and the description is omitted here.

The silicon oxide film of the present embodiment is formed by the second
For the same reason as the embodiment, the plasma CVD method, PV
The film is preferably formed by a method D or a sputtering method, and particularly preferably formed by a plasma CVD method.

In order to manufacture the gas barrier film of the present invention, it is necessary to adjust the E ′ center density of the silicon oxide film. It is preferable to increase the input power in the above. By increasing the input power, energy is given to the silicon oxide film-forming material, so that the molecules serving as the raw material can be in a very active state, the probability of breaking the bond increases, and the E ′ center (non- This is because a film having an electron pair can be obtained.

Further, it is preferable to reduce the pressure at the time of film formation. By reducing the pressure at the time of film formation, the probability that the atoms (silicon atoms and oxygen atoms) forming the silicon oxide film collide can be reduced, and thus the film having the E ′ center (unpaired electron) can be obtained. Because you can.

Since the transparency of the vapor deposition film and the gas barrier film is the same as that described in the first embodiment, the description is omitted here.

4. Fourth Embodiment The deposited film in this embodiment is preferably a plasma CV
This is a silicon oxide film formed by the method D. In this embodiment, the silicon oxide film has a C content of 2341 ± 4 cm ⁻¹ .
It is characterized by having an IR absorption peak based on the stretching vibration of O molecules.

As described above, it is not clear why the gas barrier property is improved when having the IR absorption peak, but it can be considered as follows. That is, having an IR absorption peak indicates that CO molecules are physically adsorbed in the film, that is, the CO molecules are taken in a gaseous state.

A conventional silicon oxide film has a silicon atom (S
i) and an oxygen atom (O),
Many voids exist between the silicon atom and the oxygen atom. However, in the silicon oxide film of the present embodiment, as described above, a state in which CO molecules are taken in a gaseous state in the film, that is, between the silicon atoms and the oxygen atoms constituting the silicon oxide film. Since the gaps are filled with CO molecules, the gaps are smaller than the conventional silicon oxide film,
As a result, it is considered to have excellent gas barrier properties.

Further, when considered as described above, the CO molecules physically adsorbed in the silicon oxide film of the present embodiment, that is, the CO molecules taken in the film, are plasma CV
It is considered that the organic silicon compound used as a raw material is formed by being decomposed (oxidized) when the silicon oxide film is formed by D. And the C
O molecules are formed at the same time as the silicon oxide film is formed. If the formed silicon oxide film has many voids, physical adsorption does not occur, and the gas is directly transferred from the film to the air as a gas. It can naturally be expected that it will be released.
On the other hand, in the silicon oxide film of this embodiment, 23
Since the silicon oxide film has an IR absorption peak at 41 ± 4 cm ⁻¹ based on the stretching vibration of CO molecules, gaseous CO molecules formed as so-called by-products are physically adsorbed during the formation of the silicon oxide film. It can be considered that the silicon oxide film of this embodiment has a dense structure such that the CO molecular gas cannot diffuse out of the film. is there.

Incidentally, when considered as described above, the peak of the IR absorption based on the stretching vibration of the CO molecule is usually 2341.
Although it appears at cm ⁻¹ , it is set to 2341 ± 4 cm ⁻¹ in the present invention in consideration of the resolution of the apparatus when performing IR measurement.

Here, in IR measurement, 2341 ± 4
In order to have an IR absorption peak based on the stretching vibration of CO molecules at cm ⁻¹ , it is advisable to increase the power supplied to the plasma generating means when forming a silicon oxide film by plasma CVD. This is because the breaking of bonds in the molecules of the organic silicon compound used as a raw material of the silicon oxide film can be promoted, and CO molecules are easily formed.
Further, the CO molecules may be easily formed by adjusting the flow ratio of the organic silicon compound as a raw material and oxygen.

In the IR measurement, 2341 ±
I based on the stretching vibration of the CO molecule appearing at 4 cm ^-1
The intensity of the R absorption peak is determined by the absorbance (Absorbanc).
In e), it is preferably 0.005 to 0.3. This is because, if the absorbance within the above range can be confirmed, it is clear that gaseous CO molecules are physically adsorbed in the silicon oxide film.

In the present embodiment, the IR absorption is measured and evaluated with an infrared spectrophotometer for measuring IR. Preferably, an infrared absorption spectrum is measured by attaching an ATR (multiple reflection) measuring device to the infrared spectrophotometer. At this time, it is preferable to use a germanium crystal for the prism and measure at an incident angle of 45 degrees.

The thickness of the deposited film of the present invention is the same as the description of the thickness of the silicon oxide film in the first embodiment, and the description is omitted here.

The method for manufacturing a silicon oxide film according to the present embodiment can be manufactured by the same method as the method for manufacturing a silicon oxide film according to the first embodiment.

The transparency in the case of forming a vapor deposition film and a gas barrier film is also the same as that described in the first embodiment, and the description is omitted here.

5. Combination of Embodiments In the present invention, even in the case of a gas barrier film using a vapor deposition layer having two or more types of characteristics among the characteristics of the vapor deposition layers shown in the first embodiment to the fourth embodiment. Good.

B. Substrate Next, the substrate constituting the gas barrier film of the present invention will be described.

The substrate in the gas barrier film of the present invention is not particularly limited as long as it can hold the above-mentioned vapor-deposited film having barrier properties.
Any film can be used.

Specifically, a homopolymer such as ethylene, polypropylene, butene or a polyolefin such as a copolymer or copolymer (P
O) resin, amorphous polyolefin resin (APO) such as cyclic polyolefin, polyester resin such as polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), nylon 6, nylon 12, copolymerized nylon (PA) resin such as polyvinyl alcohol (PV)
A) Resin, ethylene-vinyl alcohol copolymer (EV
OH) and other polyvinyl alcohol resins, polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) Resin, polycarbonate (PC) resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE),
Ethylene trifluoride chloride (PFA), ethylene tetrafluoride
Perfluoroalkyl vinyl ether copolymer (FE
P), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether-copolymer (EPA)
And the like.

In addition to the above resins, a resin composition comprising an acrylate compound having a radically reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group,
It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyether acrylate is dissolved in a polyfunctional acrylate monomer, or a mixture thereof. Further, a resin film obtained by laminating one or more of these resins by means such as lamination and coating can be used as the base film.

The substrate of the present invention using the above-mentioned resins and the like may be an unstretched film or a stretched film.

The substrate of the present invention can be produced by a conventionally known general method. For example, a resin as a material is melted by an extruder, extruded by an annular die or a T die, and quenched, whereby a substantially amorphous, unoriented, unstretched substrate can be produced. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like, in the flow direction (vertical axis) of the base material, or A stretched base material can be manufactured by stretching in a direction (horizontal axis) perpendicular to the flow direction of the base material. The stretching ratio in this case can be appropriately selected according to the resin used as the raw material of the base material, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

The base material of the present invention may be subjected to a surface treatment such as a corona treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment, a chemical treatment, etc., before forming the deposited film.

Further, an anchor coat agent layer may be formed on the surface of the substrate of the present invention for the purpose of improving the adhesion to the deposited film. As the anchor coating agent used in this anchor coating agent layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin,
A modified styrene resin, a modified silicone resin, an alkyl titanate, or the like can be used alone or in combination of two or more. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and the solvent, diluent and the like are dried and removed to perform anchor coating. be able to. The amount of the above-mentioned anchor coating agent to be applied may be set to 0.1.
About 1 to 5 g / m ² (dry state) is preferable.

As the base material, a long product wound up in a roll shape is convenient. The thickness of the base material cannot be specified unconditionally because it varies depending on the use of the obtained gas barrier film, but when used as a base material for general packaging materials or packaging materials, the thickness is preferably 3 to 188 μm.

C. Production Method The gas barrier film of the present invention is, as described above,
Either one of the vapor-deposited films of one embodiment or a vapor-deposited film having a plurality of features of these embodiments at the same time is formed on a substrate. Various methods can be used for forming the vapor deposition layer as described above. However, in any of the embodiments, it is particularly preferable that the film is formed by the plasma CVD method.

The preferred film forming conditions for this plasma CVD method are as follows: first, the temperature of the substrate during film formation is -20 to 100;
° C, preferably within the range of -10 to 30 ° C.

Next, an organic silicon gas and a gas containing oxygen atoms are used as raw material gases, and the flow rate ratio between the organic silicon compound gas and the gas containing oxygen atoms is 3 when the organic silicon compound gas is 1. ~ 50, preferably 3 ~
10 is set.

The effect can be further enhanced by setting a large input power per unit area in the plasma generating means of the plasma CVD apparatus or forming a space for confining plasma such as a magnet to enhance the reactivity.

In the present invention, among the raw material gases, the organic silicon compound gas includes hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), vinyltrimethoxy Silane, vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexamethyldi In addition to preferably using silazane, one or two or more conventionally known compounds such as tetramethyldisiloxane and normal methyltrimethoxysilane can be used.

However, in the present invention, SiO 2
_For the purpose of forming a _2- like film, carbon-
An organosilicon compound having no silicon bond is preferably used. Specifically, tetramethoxysilane (TMOS),
Methyltrimethoxysilane, methyldimethoxysilane,
Examples include tetraethoxysilane (TEOS), methyltriethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and methyldiethoxysilane. Among them, tetramethoxysilane (TMOS) having no carbon-silicon bond in the molecule, and It is preferable to use tetraethoxysilane (TEOS).

The gas containing an oxygen atom includes N ₂
O, oxygen, CO, CO _{2 and the} like can be mentioned. Among them, oxygen gas is preferably used.

As described above, an organic compound having no carbon-silicon bond is used as the organic silicon compound gas in the raw material gas, and the temperature of the base material at the start, the flow ratio of the raw material gas, and By setting the input power in the plasma generation means within the above-described range, a gas barrier film having better gas barrier properties can be obtained because the decomposability of the organosilicon compound gas is increased and oxygen atoms are incorporated into the film. This is presumably due to the fact that a film like SiO ₂ is formed as a result.

In the present invention, the gas barrier film thus obtained is preferably subjected to a heat treatment in the range of 50 ° C. to 200 ° C. By further heat-treating the silicon oxide film thus obtained, a silicon oxide film having better gas barrier properties can be obtained.

In the present invention, when performing this heat treatment,
2234 ± 4cm before heat treatment ^-1Expansion and contraction of CO molecules
Field of silicon oxide film with IR absorption peak due to vibration
(In the case of the fourth embodiment), the expansion and contraction of the CO molecule
Until the peak of IR absorption due to vibration disappears
Is preferred.

As described above, heating until the peak of IR absorption based on the stretching vibration of CO molecules at 2341 ± 4 cm ^-1 disappears is because the vibration of molecular bonding becomes severe by applying thermal energy to the film, Is formed, and the trapped CO molecules are desorbed.
It is considered that the bonding becomes tighter due to the omission of the O molecule, and a more dense film is formed. Therefore, it is considered that the gas barrier property is further improved by heating until the peak disappears. . Here, “there is no peak” means that the state is below the detection limit of the analyzer.

As described above, the specific heating time until the above-mentioned peak disappears greatly varies depending on the temperature. However, if the heating time is 50 ° C. or more, heating for about 30 minutes or more is required. If so, heating for 5 minutes or more is required.

D. Gas barrier film The gas barrier film of the present invention has an oxygen permeability of 0.5 c.
c / m ² / day or less and water vapor transmission rate is 0.5 g / m ² /
day or less, more preferably 0.1 cc /
m ² / day or less in water vapor transmission rate of 0.1g / m ² / da
It exhibits extremely excellent gas barrier properties of y or less. Since the gas barrier film of the present invention hardly permeates oxygen and water vapor which cause changes in the quality of the contents, applications requiring high gas barrier properties, such as packaging materials for foods and pharmaceuticals and packaging materials for electronic devices, etc. Can be preferably used. Further, since it has both high gas barrier properties and impact resistance, it can be used, for example, as a base material for various displays. Further, it can be used as a cover film of a solar cell.

E. Laminated Material By laminating another layer on the above-described gas barrier film to form a laminated material, the gas barrier film can be developed for various uses as described above. The other layers laminated here can be of various types depending on the intended use, and are not particularly limited, but a laminated material capable of effectively utilizing the characteristics of the gas barrier film described above. As a fifth embodiment, a heat-sealing resin layer is laminated on the gas barrier film,
A sixth embodiment in which a conductive layer is laminated and a sixth embodiment will be described below.

1. Fifth Embodiment (Laminated Material) FIG. 4 is a schematic sectional view showing a fifth embodiment of the present invention. In FIG. 4, a laminated material 11 includes a gas barrier film 1 having a vapor deposition layer 3 on one surface of a substrate 2, and an anchor coat agent layer and / or an adhesive layer 12 on the vapor deposition layer 3 of the gas barrier film 1. And a heat-sealable resin layer 13 formed.

For the anchor coating agent layer 12 constituting the laminated material 11, for example, an organic titanium anchor coating agent such as alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like is used. Can be formed. The formation of the anchor coat agent layer 12 is performed by coating the above-mentioned anchor coat agent with a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like. Drying and removal can be performed. The coating amount of the above anchor coating agent is 0.1 to 5 g / m.
^{About 2} (dry state) is preferable.

Further, the adhesive layer 12 constituting the laminated material 11
For example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acryl-based, polyvinyl acetate-based, polyolefin-based, casein, wax,
It is formed by using various types of laminating adhesives such as a solvent type, an aqueous type, a non-solvent type, or a hot-melt type which mainly contains a vehicle such as an ethylene- (meth) acrylic acid copolymer or a polybutadiene type. be able to. The adhesive layer 12 is formed by coating the above-mentioned laminating adhesive with, for example, a roll coat, a gravure coat, a knife coat, a deb coat, a spray coat, or another coating method, and drying and removing a solvent, a diluent, and the like. You can do it. The amount of the laminating adhesive applied is preferably about 0.1 to 5 g / m ² (dry state).

Examples of the heat-sealing resin used for the heat-sealing resin layer 13 constituting the laminated material 11 include resins that can be melted by heat and fused to each other.
Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as an acid, fumaric acid, and itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin, and the like can be used. The heat-sealable resin layer 13 may be formed by applying the heat-sealable resin as described above, or may be formed by laminating a film or sheet made of the heat-sealable resin as described above. . The thickness of such a heat-sealing resin layer 13 can be set within a range of 5 to 300 μm, preferably 10 to 100 μm.

FIG. 5 is a schematic sectional view showing another example of the laminated material in this embodiment. In FIG.
Is a gas barrier film 1 having a vapor deposition layer 3 on one surface of a base material 2, and a heat sealing property formed on the vapor deposition layer 3 of the gas barrier film 1 via an anchor coat agent layer and / or an adhesive layer 22. The gas barrier film 1 includes a resin layer 23 and a substrate layer 24 provided on the other surface (the surface on which the vapor deposition layer is not formed) of the substrate 2 of the gas barrier film 1.

The anchor coat agent layer, the adhesive layer 22 and the heat-sealing resin layer 23 constituting the laminated material 21
It can be the same as the anchor coat agent layer, the adhesive layer 12 and the heat-sealable resin layer 13 that constitute the laminated material 11 described above, and the description is omitted here.

As the base material layer 24 constituting the laminated material 21, for example, when the laminated material 21 constitutes a packaging container,
Since the base material layer 24 is a basic material, it has excellent properties in mechanical, physical, chemical, etc., and in particular, a resin film having strength, toughness, and heat resistance. Or sheets can be used. Specifically, stretching of strong resin such as polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. (uniaxial or biaxial) Or an unstretched film or sheet can be mentioned. The thickness of the base layer 24 is 5 to 100 μm,
Preferably, it is about 10 to 50 μm.

In the present embodiment, the base material layer 24
In addition, for example, a desired printing pattern such as a character, a figure, a symbol, a pattern, and a pattern may be subjected to front printing or back printing by a normal printing method. Such characters and the like can be visually recognized very well through the transparent barrier film 1 because the transparent barrier film 1 constituting the laminated material 21 has excellent transparency.

Further, in this embodiment, for example, various paper base materials constituting a paper layer can be used as the base material layer 24. Specifically, it is a paper substrate having shapeability, bending resistance, rigidity, etc., for example, a strong size bleached or unbleached paper substrate, or pure white roll paper, kraft paper, paperboard, processed Paper substrates such as paper can be used. Examples of such paper substrates, of the order of a basis weight of about 80~600g / m ^2, preferably, it is desirable to use of about a basis weight of about 100~450g / m ^2.

In the present embodiment, the base material layer 24 may be used in combination with the above-mentioned resin film or sheet and the above-mentioned paper base material.

FIG. 6 is a schematic sectional view showing another example of the laminated material of this embodiment. In FIG.
The heat barrier formed on the transparent barrier film 1 provided with the vapor deposition layer 3 on one surface of the substrate 2 and the anchor coat agent layer and / or the adhesive layer 32 on the vapor deposition layer 3 of the transparent barrier film 1 A sealing resin layer 33, a base layer 34 provided on the other surface (non-deposited layer forming surface) of the base 2 of the gas barrier film 1, and a heat sealing resin layer 35 formed on the base layer 34 And

The anchor coat agent layer, the adhesive layer 32 and the heat-sealing resin layers 33 and 3 constituting the laminated material 31
5 can be the same as the anchor coat agent layer, the adhesive layer 12 and the heat-sealable resin layer 13 that constitute the laminated material 11 described above, and the base material layer 34 that constitutes the laminated material 31 Since it can be the same as the base material layer 24 of the laminated material 21 described above, the description here is omitted.

The laminated material in this embodiment further includes, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene Resin film or sheet such as propylene copolymer, or resin film or sheet such as polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, etc. Films or sheets of various colored resins having a light-shielding property, which are formed by adding a colorant such as above and other desired additives and kneading to form a film, can be used.

These materials can be used alone or in combination of two or more, and the thickness is optional.
Usually, it is about 5 to 300 μm, preferably about 10 to 100 μm.

Further, when the laminated material of this embodiment is used for a packaging container, the packaging container is usually subjected to severe physical and chemical conditions. Strict packaging suitability is required. Specifically, various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, and the like are required. For the laminated material, a material satisfying the above-mentioned various conditions can be arbitrarily selected and used as the base material 2, the base material layers 24 and 34, or other constituent members. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate Polymer,
Ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) Acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin resin,
Polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. can do. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used.

The above film or sheet is unstretched,
Any of those uniaxially or biaxially stretched can be used. The thickness is arbitrary,
It can be used by selecting from a range of about several μm to 300 μm, and the lamination position is not particularly limited. In the present invention, the film or sheet is formed by extrusion film formation,
Any film such as an inflation film or a coating film may be used.

The laminates in this embodiment, such as the laminates 11, 21 and 31 described above, can be formed by laminating ordinary packaging materials, for example, wet lamination, dry lamination, solventless dry lamination, and extrusion. It can be manufactured using a lamination method, a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, a co-extrusion inflation method, or the like.

When performing the above-mentioned lamination, the film may be subjected to a pretreatment such as a corona treatment and an ozone treatment, if necessary. For example, an isocyanate-based (urethane-based), polyethyleneimine-based Use a known adhesive such as a polybutadiene-based, organic titanium-based anchor coating agent, or a polyurethane-based, polyacryl-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based laminating adhesive, or the like. be able to.

(Packaging Container) Next, a packaging container using the above laminated material will be described. This packaging container is a bag made or box-formed by heat fusion using the laminated material of the fifth embodiment.

Specifically, when the packaging container is a soft packaging bag, the heat-sealing resin layer of the laminated material of the fifth embodiment may be folded with the surfaces thereof facing each other, or two laminated materials of the present invention may be used. And seal the peripheral end thereof with, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope seal type, a gas seal seal type (pillow seal type), a fold seal type, and a flat bottom. Seal type, square bottom seal type,
Various forms of packaging containers according to the present invention can be manufactured by forming a sealed portion by heat fusion using other heat sealing forms.

In the above, the heat fusion can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like.

FIG. 7 is a perspective view showing an example of such a packaging container. In FIG. 7, the packaging container 51
A set of laminated materials 11 of the present invention is overlapped so that the heat-sealing resin layers 13 face each other, and in this state, heat sealing is performed on three sides of a peripheral portion to form a seal portion 52. This packaging container 51 can be filled with contents from an opening 53 formed on the other one of the peripheral portions. Then, after filling the contents, the opening 53
Is heat-sealed to form a seal portion, whereby a packaging container filled with contents can be obtained.

In addition to the above, the packaging container of the present invention may be, for example, a self-supporting packaging bag (standing pouch) or the like. Further, a tube container or the like may be manufactured using the laminated material of the present invention. Can be.

In the present invention, for example, a one-piece type, a two-piece type, another pouring spout, or a zipper for opening and closing can be arbitrarily attached to the above-mentioned packaging container.

When the packaging container of the present invention is a liquid-filled paper container containing a paper substrate, a blank for producing a desired paper container using the laminated material of the present invention in which the paper substrate is laminated is used. Make a board, using this blank board, trunk, bottom,
By forming the head or the like, for example, a brick type, flat type or Goebel top type liquid paper container or the like can be manufactured. Moreover, the shape can be manufactured by any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

FIG. 8 is a perspective view showing an example of the above-mentioned liquid-filled paper container which is a packaging container of the present invention, and FIG.
It is a top view of the blank board used for the container for enclosure shown in FIG. The blank plate 70 uses, for example, the laminated material 31 of the present invention shown in FIG. 6, and includes pressing lines m, m... For bending in forming a container and a trunk forming the trunk 62 of the container 61. Panels 71, 72, 73, 74 and container 6
The top panels 71a, 72a, 7 constituting the top 63 of the first
3a, 74a, a bottom panel 71b, 72b, 73b, 74b constituting a bottom 64 of the container 61, and a heat-sealing panel 75 for forming a cylindrical body. This blank plate 70 is bent by pressing lines m, m,..., And the inside of the end of the body panel 71 and the outside of the heat-sealing panel 75 are heat-sealed to form a cylindrical body, and thereafter, the bottom panel 71b , 72b, 73b, 74
b is bent by pressing lines m, m,... and is heat-sealed and filled with liquid from the top opening, and then the top panels 71a, 72
a, 73a, 74a are bent by pressing lines m, m,.
It can be 1.

The packaging container of the present invention is used for filling and packaging of various articles such as various foods and beverages, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and the like. Things.

[0135] 2. Sixth Embodiment (Laminated Material) A sixth embodiment of the present invention is a laminated material characterized in that a conductive layer is formed on at least one surface of the gas barrier film. FIG.
Shows an example of the present embodiment. The laminated material according to the present embodiment is obtained by forming a conductive layer 41 on a gas barrier film 1 including a base material 2 and a deposited film (silicon oxide film) 3 formed on the base material 2. As shown in FIG. 10, an anchor coat agent layer 42 for improving the adhesion of the deposited film 3 may be formed between the deposited film 3 and the substrate 2 as described above. Further, the overcoat layer 43 may be formed on the vapor deposition layer 3.

The gas barrier film 1 used in this embodiment is the same as the above-described gas barrier film, and the description is omitted here.

The conductive layer 41 used in this embodiment is
For example, an ITO film is used, and these are formed by a sputtering method, a PVD method, or an ion plating method. In the present embodiment, an ITO film obtained by a sputtering method is particularly preferable in order to obtain in-plane uniformity of conductivity.

Although the thickness of the conductive layer 41 varies greatly depending on the composition and use, it is usually 100 nm.
It is formed within a range of 200 nm.

This conductive layer 41 has a resistance value of 0 to 50 Ω.
/ □, preferably having characteristics such that the total light transmittance is 85% or more.

Such a conductive layer 41 can be used as a transparent electrode for driving a liquid crystal in a liquid crystal display device, for example.

Further, as the overcoat layer 43 used in the present invention, an ultraviolet cured film of an epoxy acrylate prepolymer having a melting point of 50 ° C. or higher or a urethane acrylate prepolymer having a melting point of 50 ° C. or higher can be used. As long as the properties for display media can be satisfied, a thermosetting type that is more thermally stable may be used. However, an ultraviolet curable resin excellent in productivity is more preferable. Naturally, adhesion to the polymer film or the inorganic layer is indispensable, and it is necessary to have excellent flexibility and chemical resistance. For this purpose, a conventional primer layer may be provided.

(Image Display Medium) The image display medium of the present invention uses the laminated material shown in the sixth embodiment as a base material,
An image display layer is formed on the conductive layer.

Examples of such an image display device include a non-light-emitting display, such as a liquid crystal display device, which performs display by giving gradation by shuttering the brightness of a backlight, a plasma display (PDP), and a field emission device. Examples of the display include a self-luminous display that performs display by illuminating a phosphor with some energy, such as a display (FED) and an electroluminescence display (EL).

When the image display medium is a liquid crystal display device, the image display layer indicates a liquid crystal layer. When the image display medium is a self-luminous display as described above, a phosphor is used. The phosphor layer has the image display layer.

Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and has substantially the same configuration as the technical idea described in the scope of the claims of the present invention. It is included in the technical scope of the invention.

[0146]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below. As described above, in the gas barrier film of the present invention, the vapor-deposited film formed on the base material has a thickness of 4 mm. There are two embodiments. Hereinafter, examples and comparative examples will be described for each embodiment.

[0147] 1. First Embodiment (Example 1-1) As shown in FIG. 11, as a base material 20, a sheet-shaped (30 cm × 21 cm) biaxially stretched polyamide film (manufactured by Toyobo Co., Ltd., N1102, thickness 15 μm)
m) was prepared and mounted on the lower electrode 114 side in the chamber 102 of the plasma CVD apparatus 101. Next, CVD
In the chamber 102 of the apparatus 101, the ultimate vacuum degree is 3.0 × 10 ⁻⁵ by an oil rotary pump and a turbo molecular pump.
The pressure was reduced to Torr (4.0 × 10 ⁻³ Pa). Also,
Hexamethyldisiloxane (H
MDSO) gas (Toray Dow Corning Silicone)
Co., Ltd., SH200, 0.65CSt) and oxygen gas (Taiyo Toyo Oxygen Co., Ltd., purity 99.9999% or more) were prepared.

Next, power having a frequency of 90 kHz (input power: 300 W) was applied to the lower electrode 114. An HMDSO gas of 1 sccm, an oxygen gas of 10 sccm, and a helium gas of 30 sccm are introduced from a gas inlet 109 provided in the vicinity of the electrode in the chamber 102, and a valve 113 between the vacuum pump 108 and the chamber 102 is opened and closed. By controlling the degree, the pressure in the film forming chamber is set to 0.25 Torr (33.325 Pa).
, And a silicon oxide film as the vapor deposition film 3 was formed on the base film 2. Where sccm is standard cub
ic cm per minute. Film formation was performed until the film thickness became 100 nm, and a gas barrier film of Example 1-1 was obtained.

Example 1-2 As shown in FIG. 12, a roll-shaped biaxially stretched polyamide film (N1102, manufactured by Toyobo Co., Ltd., thickness 15 μm, width 600
mm and a length of 5000 m), and a chamber 202 of a plasma CVD apparatus 201 provided with a winding mechanism.
Mounted inside. Next, the chamber 2 of the CVD apparatus 201
02, the ultimate vacuum degree is 3.0 × 10 ⁻⁵ Torr (4.0 × 10 ⁻³ P) by an oil rotary pump and an oil diffusion pump.
The pressure was reduced until a). In addition, tetramethoxysilane (TMOS) gas (Shin-Etsu Chemical Co., Ltd.)
Co., Ltd., KBM04) and oxygen gas (Taiyo Oriental Oxygen)
(Purity: 99.9999% or more).

Next, one electrode 213 is arranged near the coating drum 205 so as to face the coating drum 205, and a high-frequency power (frequency power: 40 kHz) having a frequency of 40 kHz is provided between the coating drum 205 and the electrode 213. 3.0 kW). The gas inlet 2 provided near the electrode 213 in the chamber 202
From 09, the TMOS gas was 50 sccm and the oxygen gas was 5 sccm.
The pressure in the chamber at the time of film formation was set to 5 × 10 ⁻² To ² by controlling the degree of opening and closing of a valve 214 between the vacuum pump 208 and the chamber 202 by introducing the pressure at 00 sccm.
At rr (6.7 Pa), a silicon oxide film was formed on the base film 40 as a deposition film. Base film 40
Was set such that the thickness of the silicon oxide film was 100 nm, and a gas barrier film of Example 1-2 was obtained.

(Example 1-3) The thickness of the silicon oxide film was 10
A gas barrier film of Example 3 was obtained in the same manner as in Example 2, except that the traveling speed of the base film was set to be nm.

(Comparative Examples 1-1 to 1-5) Hexamethyldisiloxane gas and oxygen gas were introduced under the conditions shown in Table 1,
Comparative Examples 1-1 to 1-1 were formed under the same conditions as in Example 1 except that the flow rates, flow ratios, and film forming pressures of those gases were adjusted.
-5 gas barrier film was obtained.

(Evaluation Method) The component of the silicon oxide film was ESC
A (manufactured by VG Scientific, UK, ESCA
LAB220i-XL). As an X-ray source, Ag-3d-5 / 2 peak intensity, 300K-1
A monochrome AlX-ray source with Mcps and a diameter of about 1 m
An mφ slit was used. The measurement was performed in a state where the detector was set on the normal line with respect to the sample surface used for the measurement, and appropriate charging correction was performed. The analysis after measurement is based on the above ESC
Using software Eclipse version 2.1 (manufactured by VG Scientific, UK) attached to the A apparatus, using peaks corresponding to binding energies (Binding Energy) of Si: 2p, C: 1s, O: 1s. went. At this time, the background of Shirley was removed for each peak, and the sensitivity coefficient of each element was corrected (for C = 1, Si =
0.817, O = 2.930), and the atomic ratio was determined. With respect to the obtained atomic ratio, the number of Si atoms was set to 100 and the number of O and C atoms as other components was calculated and evaluated as a component ratio.

The IR measurement was performed by using a Fourier transform infrared spectrophotometer (manufactured by JASCO, Herschel) equipped with an ATR (multiple reflection) measuring device (ATR-300 / H, manufactured by JASCO).
FT / IR-610). The infrared absorption spectrum uses germanium crystals as prisms,
It was measured at an incident angle of 45 degrees.

The refractive index of the silicon oxide film was measured using an optical spectrometer (UV-3100PC, manufactured by Shimadzu Corporation). From the obtained measurement results of the transmittance and the reflectance, the optical interference method was used to evaluate the refractive index at 633 nm.

The obtained gas barrier film was subjected to oxygen gas transmission measurement and water vapor transmission measurement to evaluate gas barrier properties. The oxygen gas permeability is measured by an oxygen gas permeability measuring device (OX-TRAN 2/20, manufactured by MOCON).
Was measured under the conditions of 23 ° C. and dry (0% Rh). The water vapor transmission rate can be measured using a water vapor transmission rate measuring device (MOCO
N Company, PERMATRAN-W 3/31)
The measurement was performed at 37.8 ° C. and 100% Rh. The evaluation criterion for the gas barrier property is that the oxygen gas transmission rate (OTR) is 0.5.
cc / m ² / day or less, and a water vapor transmission rate (W
VTR) is 0.5 g / m ² / day or less.

[0157]

[Table 1]

(Measurement Results) Each of the gas barrier films of Examples 1-1 to 1-3 has an oxygen gas transmission rate (OTR).
Is 0.5 cc / m ² / day or less, and the water vapor transmission rate (WV
TR) was 0.5 g / m ² / day or less, indicating excellent gas barrier properties. On the other hand, the gas barrier films of Comparative Examples 1-1 to 1-5 showed oxygen gas transmission rates (OTR) and water vapor transmission rates. Rate (WVTR) exceeded the evaluation criteria, indicating insufficient gas barrier properties.

[0159] 2. Second Embodiment [1] When Using Plasma CVD Method (Examples 2-1 to 2-3) Examples 2-1 and 2-2 were obtained in the same manner as in Examples 1-1 to 1-3. .

(Comparative Examples 2-1 to 2-5) Hexamethyldisiloxane gas and oxygen gas were introduced under the conditions shown in Table 2 below, and the flow rates, flow ratios, and film forming pressures of these gases were adjusted. Was formed under the same conditions as in Example 2-1 to obtain gas barrier films of Comparative Examples 2-1 to 2-5.

(Method of Measuring the Distance Between Grains by Atomic Force Microscope) Grains cannot be directly measured because the surface of a deposited film produced by the above-mentioned plasma CVD method is smooth without treatment. Therefore, a surface treatment was first performed with an aqueous solution of hydrofluoric acid or ammonium fluoride. This treatment utilizes the property that the boundary dissolves, but the grain does not easily dissolve,
By performing the treatment, it was possible to observe the grains formed on the surface of the deposited film.

Then, the sample after film formation was 10 cm × 1
After cutting to a size of 0 cm, treated at 23 ° C. in a 0.5% hydrofluoric acid solution for 5 seconds, washed with water for 60 seconds,
Drying was performed.

Here, an atomic force microscope (hereinafter “AFM”)
And ) Will be described.

An AFM manufactured by Digital Instruments, Seiko Denshi, Topometrix or the like can be used for the measurement. In this case, a Nano Scope III manufactured by Digital Instruments was used. In this case, after performing flat processing on the AFM image whose surface shape is measured in the area of 500 nm × 500 nm in the tapping mode, an arbitrary cross section is observed, and two adjacent grains having almost the same peak height are observed. For, the distance between that peak and the adjacent peak was measured. In the measurement, a cantilever in a state free from wear and dirt was used, and a uniform uneven area without significant dents or protrusions was used as a measurement point.

Note that the tapping mode is defined in Q. Zon
g et al. Surface Science Letter, 1993 Vol.290, L688
As described in -690, a cantilever with a probe at the tip is vibrated near the resonance frequency (about 50 to 500 MHz) using a piezo vibrator, and the light is intermittently lightened on the sample surface. In this method, the position of the cantilever is moved in the uneven direction (Z direction) so as to keep the detected amplitude change constant, and a signal and a plane based on the movement in the Z direction are provided. This is a method for measuring a three-dimensional surface shape based on signals in directions (XY directions). Also,
The flat processing is processing for correcting inclination of a two-dimensional data with respect to a reference plane using a first-order, second-order, or three-dimensional function. This processing cancels the undulation of the entire surface.

(Measurement of Gas Permeability) The obtained gas barrier film was subjected to oxygen gas permeability measurement and water vapor permeability measurement to evaluate gas barrier properties. The oxygen gas permeability is measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-
TRAN 2/20), dry at 23 ° C. (0% R)
The measurement was performed under the condition of h). The water vapor transmission rate was measured using a water vapor transmission rate measurement apparatus (PERMATRAN-W manufactured by MOCON).
3/31) under the conditions of 37.8 ° C. and 100% Rh. The evaluation criteria for the gas barrier property are that the oxygen gas transmission rate (OTR) is 0.5 cc / m ² / day or less and the water vapor transmission rate (WVTR) is 0.5 g / m ² / day.
It was as follows.

(Measurement Results) Table 2 below shows the measurement results.

[0168]

[Table 2]

As is clear from Table 1 above, Example 2
Each of the gas barrier films -1 to 2-3 has an oxygen gas transmission rate (OTR) of 0.5 cc / m ² / day or less,
While the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less and exhibited excellent gas barrier properties, the gas barrier films of Comparative Examples 2-1 to 2-5 showed oxygen gas transmission rates (OTR ) And water vapor transmission rate (WVTR) exceeded the evaluation criteria, and showed insufficient gas barrier properties.

[2] When Using Ion Plating Method (Example 2-4) As shown in FIG.
0 is a roll of biaxially stretched polyethylene terephthalate film (PET, 12 μm thick, manufactured by Unitika Ltd.)
m), it was mounted in a chamber 302 of a wind-up horocathode ion plating apparatus 301. Next, silicon dioxide (Merck Japan KK) was used as an evaporation source.
(Purity: 99%, particle size: 2.5 to 4 mm), and mounted on an anode (hearth) 306. Next, the chamber 302
The inside was evacuated to an ultimate vacuum of 1 × 10 ⁻⁵ Torr by an oil rotary pump and an oil diffusion pump.

Next, by controlling the opening / closing degree of the valve 309 between the vacuum pump 308 and the chamber,
While maintaining the chamber pressure at the time of film formation at 5 × 10 ⁻⁴ Torr, the substrate film was run and the argon gas was 20 scc.
5kW of electric power for plasma generation is applied to the hollow cathode type plasma gun 307 into which m has been introduced.
The evaporation source was evaporated by converging and irradiating the plasma flow on the evaporation source on 306, and the evaporated molecules were ionized by high-density plasma to form a silicon oxide film as a deposition film on the base film 50. The running speed of the base film 50 is such that the thickness of the formed silicon oxide film is 100 nm.
It was set to be.

(Example 2-5) A film was formed under the same conditions as in Example 2-4 except that oxygen gas introduced during film formation was introduced at 10 sccm to obtain a gas barrier film of Example 2-5. Was.

(Comparative Example 2-6) The input power at the time of film formation was set at 3.
A film was formed under the same conditions as in Example 2-4 except that the power was set to 5 kW to obtain a gas barrier film of Comparative Example 2-6.

(Comparative Example 2-7) A film was formed under the same conditions as in Example 2-4 except that the chamber pressure during film formation was set to 1 × 10 ⁻³ Torr. A gas barrier film was obtained.

(Measurement of Gas Permeability) The obtained gas barrier film was subjected to oxygen gas permeability measurement and water vapor permeability measurement to evaluate gas barrier properties. The oxygen gas permeability is measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-
TRAN 2/20), dry at 23 ° C. (0% R)
The measurement was performed under the condition of h). The water vapor transmission rate was measured using a water vapor transmission rate measurement apparatus (PERMATRAN-W manufactured by MOCON).
3/31) under the conditions of 37.8 ° C. and 100% Rh. The evaluation criteria for the gas barrier property are that the oxygen gas transmission rate (OTR) is 0.5 cc / m ² / day or less and the water vapor transmission rate (WVTR) is 0.5 g / m ² / day.
It was as follows.

(Measurement Results) The following Table 3 shows the measurement results.

[0177]

[Table 3]

As is clear from Table 3 above, Example 2
Each of the gas barrier films of -4 to 2-5 has an oxygen gas transmission rate (OTR) of 0.5 cc / m ² / day or less,
While the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less and exhibited excellent gas barrier properties, the gas barrier films of Comparative Examples 2-6 to 2-7 showed oxygen gas transmission rates (OTR ) And water vapor transmission rate (WVTR) exceeded the evaluation criteria, and showed insufficient gas barrier properties.

[3] When Using Sputtering Method (Example 2-6) 10 cm × 10 c as base film
m-size sheet-shaped biaxially stretched polyethylene terephthalate film (manufactured by Unitika Ltd., PET, thickness 12 μm)
m) was mounted in a chamber of a batch-type sputtering film forming apparatus (manufactured by Anelva, SPF-730H). Next, Si (purity of 99.9999% or more) was prepared as a sputter target material and mounted in the chamber. Next, argon gas (Taiyo Oriental Oxygen Co., Ltd., purity of 99.9999% or more) and oxygen gas (Taiyo Toyo Oxygen Co., Ltd., purity of 99.9999% or more) are used as additive gases during film formation.
Was prepared.

Next, the pressure in the chamber was reduced to an ultimate vacuum of 2 × 10 ⁻³ Pa or less by an oil rotary pump and a cryopump. Next, 30 sccm of argon gas and 5 sccm of oxygen gas were introduced, and by controlling the opening / closing degree of a valve between the vacuum pump and the chamber, the chamber pressure at the time of film formation was kept at 0.1 Pa, and the DC magnetron sputtering method was used. Then, a silicon oxide film as a deposition film was formed at an input power of 200 W. The film formation time was set so that the thickness of the silicon oxide film was 100 nm.
Was obtained.

(Example 2-7) The film forming pressure was 0.05 Pa
Was formed under the same conditions as in Example 2-6 except that the gas barrier film of Example 2-7 was obtained.

(Example 2-8) A film was formed under the same conditions as in Example 2-6 except that the input power was set to 400 W, to obtain a gas barrier film of Example 2-8.

(Comparative Example 2-8) The oxygen gas flow rate was set to 15 sc
The film was formed under the same conditions as in Example 2-6 except that the gas barrier film was set to cm. Thus, a gas barrier film of Comparative Example 2-8 was obtained.

(Comparative Example 2-9) The argon gas flow rate was set to 60.
Except for setting to sccm, film formation was performed under the same conditions as in Example 2-6 to obtain a gas barrier film of Comparative Example 2-9.

(Measurement of Gas Permeability) The obtained gas barrier film was subjected to oxygen gas permeability measurement and water vapor permeability measurement to evaluate gas barrier properties. The oxygen gas permeability is measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-
TRAN 2/20), dry at 23 ° C. (0% R)
The measurement was performed under the condition of h). The water vapor transmission rate was measured using a water vapor transmission rate measurement apparatus (PERMATRAN-W manufactured by MOCON).
3/31) under the conditions of 37.8 ° C. and 100% Rh. The evaluation criteria for the gas barrier property are that the oxygen gas transmission rate (OTR) is 0.5 cc / m ² / day or less and the water vapor transmission rate (WVTR) is 0.5 g / m ² / day.
It was as follows.

(Measurement results) The following Table 4 shows the measurement results.

[0187]

[Table 4]

As apparent from Table 4 above, Example 2
Each of the gas barrier films of -6 to 2-8 has an oxygen gas transmission rate (OTR) of 0.5 cc / m ² / day or less,
While the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less and showed excellent gas barrier properties, the gas barrier films of Comparative Examples 2-8 to 2-9 showed oxygen gas transmission rates (OTR ) And water vapor transmission rate (WVTR) exceeded the evaluation criteria, and showed insufficient gas barrier properties.

[0189] 3. Third Embodiment (Examples 3-1 to 3-3) The gas barrier films of Examples 3-1 to 3-3 were obtained using the same method as in Examples 1-1 to 1-3.

(Comparative Examples 3-1 to 3-5) Example 3-
The gas barrier films of Comparative Examples 3-1 to 3-5 were obtained by basically the same method as in Example 1.

However, each parameter (flow rate of organosilicon compound (HMDSO) gas, flow rate of oxygen gas, film forming pressure, input power, film thickness) was set to the values shown in Table 5 below.

(Measurement Method of Electron Spin Resonance Method (ESR Method)) The density of the E ′ center of each silicon oxide film produced by the above-mentioned plasma CVD method was measured by the electron spin resonance method (ESR method). The equipment used for the measurement and the measurement conditions were as follows.

(Measurement device) Main device: ESR350E (manufactured by BRUKER) Auxiliary device: HP5351B Microwave frequency counter (manufactured by HEWLETTPACKEARD), ER0
35M Gauss meter (manufactured by BRUKER), ESR
910 cryostat (manufactured by OXFORD)

(Measurement conditions) Measurement temperature: room temperature (23 ° C.) Magnetic field sweep range: 331.5 to 341.5 mT Modulation: 100 kHz, 0.2 mT Microwave: 9.43 GHz, 0.1 mW Sweep time: 83.886 sec × Four times Time constant: 327.68 msec Data point: 1024 points Cavity: TM ₁₀ , cylindrical

(Analysis Method) A signal at around g = 2.00003 due to the E ′ center in the silica film was observed. The ESR spectrum is usually obtained as a differential curve,
Absorption curve by one derivative, signal intensity by two derivatives (area intensity)
Is obtained. The spin number represents the number of unpaired electrons and is a value obtained from the signal intensity using a polyethylene film into which ions have been implanted as a secondary standard sample. Note that copper sulfate pentahydrate was used as the primary standard sample.

The number of E 'center spins normalized by the film thickness and the measurement area is obtained as the density of the E' center. In addition, the detection limit of the E ′ center in the above apparatus (the apparatus used in Examples and Comparative Examples) was 5 × 10 ¹⁵
spins / cm ³ .

(Measurement results) The following Table 5 shows the measurement results.

[0198]

[Table 5]

As apparent from Table 5 above, Example 3
Each of the gas barrier films of -1 to 3-3 has an oxygen gas permeability (OTR) of 0.5 cc / m ² / day or less,
While the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less and exhibited excellent gas barrier properties, the gas barrier films of Comparative Examples 1 to 5 showed an oxygen gas transmission rate (O
TR) and water vapor transmission rate (WVTR) both exceeded the evaluation criteria, and showed insufficient gas barrier properties.

[0200] 4. Fourth Embodiment (Examples 4-1 to 4-3) The gas barrier films of Examples 4-1 to 4-3 were obtained using the same method as in Examples 1-1 to 1-3.

(Comparative Examples 4-1 to 4-5) Example 4-
The gas barrier films of Comparative Examples 4-1 to 4-5 were obtained by basically the same method as in Example 1.

However, each parameter (flow rate of organosilicon compound (HMDSO) gas, flow rate of oxygen gas, deposition pressure, input power, film thickness) was set to the values shown in Table 6 below.

(IR Measurement) The IR measurement was performed by using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, He, equipped with an ATR (multiple reflection) measuring device (ATR-300 / H, manufactured by JASCO Corporation).
rschel FT / IR-610). The infrared absorption spectrum was measured using a germanium crystal as the prism at an incident angle of 45 degrees.

(Evaluation Results) The obtained gas barrier film was measured for oxygen gas permeability and water vapor permeability to evaluate gas barrier properties. The oxygen gas permeability is measured using an oxygen gas permeability measurement device (OX-TRAN, manufactured by MOCON).
2/20) under the conditions of 23 ° C. and dry (0% Rh). The water vapor transmission rate was measured using a water vapor transmission rate measuring apparatus (PERCONTRAN-W 3/3 manufactured by MOCON).
Using 1), the measurement was performed under the conditions of 37.8 ° C. and 100% Rh. The evaluation criteria for gas barrier properties are oxygen gas permeability (OT
R) was 0.5 cc / m ² / day or less, and the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less.

Table 6 below shows the evaluation results.

[0206]

[Table 6]

As is clear from Table 6 above, Example 4
Each of the gas barrier films -1 to 4-3 has an oxygen gas transmission rate (OTR) of 0.5 cc / m ² / day or less,
While the water vapor transmission rate (WVTR) was 0.5 g / m ² / day or less and showed excellent gas barrier properties, the gas barrier films of Comparative Examples 4-1 to 4-5 showed oxygen gas transmission rates (OTR ) And water vapor transmission rate (WVTR) exceeded the evaluation criteria, and showed insufficient gas barrier properties.

(Heat Treatment) The gas barrier films of Examples 4-1 to 4-3 were subjected to heat treatment under various conditions. Heating conditions and oxygen gas transmission rate (OTR)
Table 7 summarizes the evaluation results of the water vapor transmission rate (WVTR). The evaluation method is the same as the method in the example of the fourth embodiment.

[0209]

[Table 7]

As is clear from Table 7, the sample heat-treated at 40 ° C. for 60 minutes, and the sample heated at 55 ° C. for 5 minutes showed an IR based on the stretching vibration of CO molecules. An absorption peak (2341 cm ^-1 ) was present, in which case no improvement in oxygen and vapor transmission rates was seen. However, the sample heat-treated at 55 ° C. for 30 minutes and the sample heat-treated at 70 ° C. for 5 minutes are:
Peak of IR absorption based on stretching vibration of CO molecule (2341 cm
^-1 ) was below the detection limit of the analytical instrument, and oxygen permeability and vapor permeability improved.

[0211]

As described above, the gas barrier film of the present invention can be obtained not only by simply adjusting the thickness of the deposited film as in the prior art, but also by forming the composition and the surface of the deposited film acting as a gas barrier film. By controlling the distance between grains, the presence or absence of the E 'center observed by electron spin resonance (ESR) measurement, and the presence or absence of adsorbed CO molecules, a gas barrier film with extremely excellent gas barrier properties is obtained. be able to.

Further, the gas barrier film of the present invention has an oxygen permeability of 0.5 cc / m ² / day or less and a water vapor permeability of 0.5 g / m ² / day or less, and is required to have high gas barrier properties. For example, it can be preferably used for packaging materials for foods and pharmaceuticals, and packaging materials for electronic devices and the like.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of the configuration of a gas barrier film of the present invention.

FIG. 2 is a schematic cross-sectional view showing grains on the surface of a deposition layer in a second embodiment.

FIG. 3 is an enlarged view of the surface of the gas barrier film shown in FIG.

FIG. 4 is a schematic sectional view showing an example of a laminated material (a fifth embodiment) using the gas barrier film of the present invention.

FIG. 5 is a schematic sectional view showing another example of a laminated material (fifth embodiment) using the gas barrier film of the present invention.

FIG. 6 is a schematic sectional view showing another example of a laminated material (fifth embodiment) using the gas barrier film of the present invention.

FIG. 7 is a schematic plan view showing an example of a packaging container using the gas barrier film of the present invention.

FIG. 8 is a schematic perspective view showing another example of a packaging container using the gas barrier film of the present invention.

9 is a plan view of a blank plate used for manufacturing the packaging container shown in FIG.

FIG. 10 is a schematic sectional view showing an example of a laminated material (sixth embodiment) using the gas barrier film of the present invention.

FIG. 11 is a configuration diagram illustrating an example of a plasma CVD apparatus.

FIG. 12 is a configuration diagram illustrating an example of a plasma CVD apparatus provided with a winding mechanism.

FIG. 13 is a configuration diagram showing an example of a winding type hollow cathode ion plating apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Gas barrier film 2 ... Base material 3 ... Vapor deposition film 11, 21, 31 ... Laminated material 13, 23, 33 ... Heat sealing resin layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C23C 16/40 C23C 16/40 4K030 // C08L 101: 00 C08L 101: 00 (31) Priority claim number Special Application No. 2000-318014 (P2000-318014) (32) Priority date October 18, 2000 (Oct. 18, 2000) (33) Priority claiming country Japan (JP) F-term (reference) 3E060 AA03 AA05 AB04 BA06 BC01 BC04 BC06 CG12 CG30 DA20 EA03 3E064 AA01 AB03 AB11 BA03 BA05 BA07 BA21 BA22 BA24 BA36 BA37 BA54 BA60 BB03 BC08 BC18 EA18 GA04 3E086 AB02 AD01 AD02 BA04 BA15 BA33 BA40 BB02 BB05 BB35 BB90 CA01 CA28 A38F DA01 4F100 AA20B AA20C AH06B AH06C AK01D AK46 AR00E AT00A BA02 BA03 BA04 BA06 BA10B BA10C BA10D EH66B EH66C GB15 GB41 JA20 JD02 JG01E JL12D JM02B JM02C JN18B JN18C 4K030 AAA BA44 CA07 CA12 FA01 GA14 HA02 LA01 LA18 LA24

Claims (14)

[Claims] 1. A plasma CV on one or both sides of a substrate.
A gas barrier film having a silicon oxide film formed by Method D, wherein the silicon oxide film has a component ratio of 170 to 200 O atoms and 30 or less C atoms to 100 Si atoms, Further, S between 1055 and 1065 cm ^-1
A gas barrier film having IR absorption based on i-O-Si stretching vibration. 2. The silicon oxide film has a refractive index of 1.45 to 1.45.
The gas barrier film according to claim 1, wherein the gas barrier film has a ratio of 1.48. 3. A gas barrier film comprising a substrate and a vapor-deposited film formed on both sides or one side of the substrate, wherein a distance between grains formed on the vapor-deposited film surface is 5 or more.
A gas barrier film having a thickness of from 40 nm to 40 nm. 4. The gas barrier film according to claim 3, wherein the deposited film is a silicon oxide film. 5. A gas barrier film having a substrate and a silicon oxide film formed on both sides or one side of the substrate, wherein the silicon oxide film is observed by an electron spin resonance (ESR) measurement. A gas barrier film having an E ′ center. 6. The density of the E ′ center is 5 × 10 ¹⁵ s.
6. The ratio is not less than pins / cm ^3.
The gas barrier film according to the above. 7. A gas barrier film comprising a base material and a silicon oxide film formed on both sides or one side of the base material, wherein the silicon oxide film has a stretching vibration of CO molecules at 2341 ± 4 cm ^−1. A gas barrier film having an IR absorption peak based on 8. An oxygen transmission rate of 0.5 cc / m ² / day
The gas barrier film according to any one of claims 1 to 7, wherein the water vapor transmission rate is 0.5 g / m ² / day or less. 9. The silicon oxide film has a thickness of 5 to 300 n.
The gas barrier film according to any one of claims 1 to 8, wherein m is m. 10. A method for producing a gas barrier film, wherein a silicon oxide film is formed on a substrate by a plasma CVD method in a reaction chamber using a gas containing at least an organic silicon compound gas and a gas containing oxygen atoms, The component of the organosilicon compound gas is a compound having no carbon-silicon bond in the molecule, and the temperature of the base material at the start of film formation is in the range of −20 ° C. to 100 ° C. The silicon oxide film is formed by setting the flow ratio of the gas to the gas containing oxygen atoms to be in the range of 3 to 50 when the organosilicon compound gas is 1, and then in the range of 50 ° C to 200 ° C. A method for producing a gas barrier film, which comprises performing a heat treatment. 11. A laminated material, wherein a heat-sealing resin layer is provided on at least one surface of the gas barrier film according to any one of claims 1 to 9. 12. A packaging container obtained by using the laminated material according to claim 11 to form a bag or a box by heat-sealing the heat-sealing resin layer. 13. A laminated material, wherein a conductive layer is formed on at least one surface of the gas barrier film according to any one of claims 1 to 9. 14. An image display medium comprising the laminate according to claim 13 as a base material, and an image display layer formed on the conductive layer.