JP2002361774A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having extremely excellent gas barrier properties while holding a predetermined thickness of the film and further having a flexing resistance and an impact resistance. SOLUTION: The gas barrier film comprises a silicon oxide film formed by a plasma CVD method on one side surface or both side surfaces of a base. The silicon oxide film has a component ratio of O atoms of a range of 180 to 200 to Si atoms of 100, a component ratio of C atoms of 40 to 80 to Si atoms of 100. The silicon oxide film further has an IR absorption based on an Si-O-Si stretching vibration between 1,045 and 1,060 cm<-1> , and an IR absorption based on an Si-CH3 stretching vibration at 1,274±8 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 formed by a plasma CVD method.

[0002]

2. Description of the Related Art Gas barrier films are mainly used as (a) packaging materials for foods, pharmaceuticals, etc. in order to prevent the influence of oxygen, water vapor, etc., which may cause changes in the quality of contents. 2. Description of the Related Art Elements formed on a liquid crystal display panel, an EL display panel, and the like are used as a package material for an electronic device or the like in order to avoid performance degradation due to contact with water vapor. As a gas barrier film, a film to which a film having a gas barrier property is bonded and a film to which a film having a gas barrier property is formed by a wet film formation or a dry film formation are conventionally known.

As a method of dry-forming a film having a gas barrier property 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.

However, a conventional gas barrier film having a silicon oxide film formed by a plasma CVD method has two problems.
Oxygen permeability (OTR) of about cc / m ² / day, 2
It has a water vapor transmission rate (WVTR) of only about g / m ² / day and is still insufficient when used for applications having higher gas barrier properties.

When an inorganic oxide film such as a silicon oxide film is used as a barrier film, it is generally known that the gas permeability is reduced by increasing the film thickness. However, the Society of Vacuum Coaters In, JTFelts
(34th Annual Technical Conference Proceedings (19
91), p.99-104) and JEKlemberg-Sapieha et al. (36th Annua
l Technical Conference Proceedings (1993), p.445-44
9), as the film thickness increases and the internal stress of the film relaxes,
He pointed out that cracks occur in the barrier film and the gas permeability is rather increased.

On the other hand, such a gas barrier film is
As described above, there is a use as a packaging material, but it is necessary to process the film into some form before use. However, the inorganic oxide film such as the above-mentioned silicon oxide film has such a problem that the processability is poor and, when processed, the gas barrier property cannot be maintained.

[0007] In recent years, elements formed on liquid crystal display panels, EL display panels, and the like are required to have portability such as, for example, display portions of mobile phones. When used as, a certain degree of impact resistance is required. However, a gas barrier film using a conventional silicon oxide film has poor impact resistance, which may cause a problem in practical use.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has an extremely excellent gas barrier property while maintaining a film thickness at a predetermined thickness. A main object is to provide a gas barrier film having impact resistance.

[0009]

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 180 with respect to a number of Si atoms of 100.
Component ratio in the range of 200 to 200 and 1 Si atom
It consists of a component ratio of 40 to 80 C atoms to 00,
Further, between 1045 and 1060 cm ⁻¹ , Si—O—Si
IR absorption based on stretching vibration and 1274 ± 4c
A gas barrier film characterized in that m ^-1 has IR absorption based on Si—CH ₃ 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. And a gas barrier film having excellent bending resistance and impact resistance. On the other hand, if the number of C atoms exceeds the above range, an amorphous carbon film may be formed and may be easily broken.

[0011] In the first aspect of the present invention,
The silicon oxide film preferably has a refractive index of 1.50 or more and 1.70 or less. This is because by controlling the refractive index of the silicon oxide film acting as a gas barrier film within the above range, the denseness of the film itself can be improved and the gas barrier properties can be further improved.

Further, in the invention described in claim 1 or claim 2, as described in claim 3,
It is preferable that the oxygen permeability is 0.5 cc / m ² / day or less and the water vapor permeability is 0.5 g / m ² / day or less. By setting the oxygen transmission rate and the water vapor transmission rate within the above ranges, almost no oxygen and water vapor which cause a change in the quality of the content are transmitted therethrough, so that it can be preferably used for applications requiring high gas barrier properties. Because.

In the invention described in any one of the first to third aspects, as described in the fourth aspect, the silicon oxide film has a thickness of 5 to 300 nm.
It is preferable that According to the invention, 5 to 300 n
m, even when a very thin deposited film is formed,
This is because excellent gas barrier properties can be exhibited, and cracks can hardly be formed in the deposited film. 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.

In the present invention, as described in claim 5, 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 4. The present invention provides a laminated material characterized by comprising:

When such a laminated material is used, 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 this packaging container has excellent gas barrier properties, it can be suitably used as a packaging material for foods, pharmaceuticals, and electronic devices.

Further, in the present invention, as described in claim 7, a conductive layer is provided on at least one surface of the gas barrier film according to any one of claims 1 to 4. A laminated material characterized by being formed is provided. When such a laminated material is used, an image display medium can be obtained by forming an image display layer on the conductive layer as described in claim 8. 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.

[0017]

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 silicon oxide film 3 formed on both surfaces or one surface of the substrate 2. Hereinafter, this silicon oxide film, and the substrate, further divided into the method of manufacturing this gas barrier film,
Each will be described.

A. Silicon oxide film The silicon oxide film in the present invention is preferably a plasma CV
This silicon oxide film is a vapor-deposited film formed by the D method.
And a component ratio of 40 to 80 C atoms,
There is IR absorption based on Si-O-Si stretching vibration between 5~1060cm ^-1, further Si in 1274 ± 4 cm ^-1
It is characterized by having IR absorption based on —CH ₃ stretching vibration. 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.

Further, at this time, 1.50 or more and 1.70
More preferably, it is formed to have the following refractive index. The gas barrier film 1 including the silicon oxide film 3 having such characteristics has a dense structure and exhibits extremely excellent gas barrier properties.

In order to make the respective component ratios of Si, O and C equal to 180 to 200 O atoms and 40 to 80 C atoms with respect to 100 Si atoms, the flow rate ratio between the organic silicon compound gas and the oxygen gas is determined. It can be controlled by adjusting the magnitude of the input power per unit flow rate of the organosilicon compound gas. Specifically, the following method can be used.

The ratio of oxygen gas / silicon compound gas is
A method in which carbon is positively introduced into the silicon oxide film by adjusting the concentration to a range of about 0 to 10.

Unit flow rate of organic silicon gas (1 sccm)
Input power density per unit from 0.01 kW / m ² to 5 kW / m
A method in which an appropriate amount of carbon is left in the silicon oxide film by adjusting to m ² .

Since the silicon oxide film having a component composition in this range appropriately contains a Si—C bond, the silicon oxide film has extremely excellent gas barrier properties and excellent bending resistance and impact resistance.

The method of measuring the proportion of each component in the silicon oxide film is not particularly limited as long as it is a method capable of quantitatively measuring each component of Si, O, and C. As a method, ESCA (Electron spectroscop
y for chemical analysis) and RBS (Rutherford bac
k scattering), Auger electron spectroscopy, etc., and the ratio of each component can be determined based on the results measured by these methods.

When the O component ratio is less than 180,
It is often seen when the flow rate ratio of (oxygen gas / organic silicon compound gas) is small (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, and has a dense crystal structure. Therefore, it is considered that the oxygen permeability and the water vapor permeability are increased, and sufficient gas barrier properties cannot be exhibited. Note that the number of O atoms is stoichiometrically hard to exceed 200, and thus 200 is set as the upper limit.

On the other hand, if the component ratio of C is less than 40, it is not preferable because bending resistance and impact resistance obtained by appropriately introducing Si—CH ₃ bonds cannot be obtained. When the component ratio exceeds 80,
It becomes a carbon film (graphite film, amorphous carbon film) having a CC bond as a main skeleton, which is not preferable because gas barrier properties and bending resistance are reduced.

In IR measurement, 1045 to 1060c
In order to make the absorption based on the Si—O—Si stretching vibration between m ⁻¹ , the organic silicon should be set so that the component ratio of C is in the range of 40 to 80 and a dense crystal structure is obtained. It can be controlled by adjusting the flow rate ratio between the compound gas and the oxygen gas, the magnitude of the input power per unit flow rate of the organic silicon compound gas, and the like. Specifically, similarly to the above-described method for controlling the component ratio, the ratio of oxygen gas / silicon-containing compound gas is adjusted within a range of about 0 to 10 so that carbon is positively contained in the silicon oxide film. a method of introducing into, by adjusting the input power density per unit organosilicon gas flow (1 sccm) from 0.01 kW / m ² to 5 kw / m ^2, or a method to leave an appropriate amount of carbon in the silicon oxide film Can be mentioned.

The silicon oxide film exhibiting such IR absorption is:
Since it has an appropriate Si—CH ₃ bond and keeps the crystal structure dense, it has excellent gas barrier properties and also has bending resistance and impact resistance.

The IR absorption is measured and evaluated with an infrared spectrophotometer for IR measurement. 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.

When there is no IR absorption in this range, it is often observed that the flow ratio of (oxygen gas / organic silicon compound gas) is not within the proper range or that the input power per unit flow rate of the organic silicon compound gas is not proper. As a result, although C is contained, a dense crystal structure cannot be obtained. As a result, oxygen permeability and water vapor permeability are large, and sufficient gas barrier properties cannot be exhibited.

The refractive index of the silicon oxide film is set to 1.50 to 1.70.
Can be controlled by adjusting the flow rate 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. Specifically, the method used for adjusting the position of the IR absorption can be exemplified.

The 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 1.50, the formed silicon oxide film becomes sparse, the oxygen transmittance and the water vapor transmittance increase, and a sufficient gas barrier property cannot be exhibited. On the other hand, when the refractive index exceeds 1.70, the amount of C (carbon) introduced is too large, and as a result, the formed silicon oxide film becomes sparse, and the oxygen permeability and the water vapor permeability are reduced. It becomes too large to exhibit sufficient gas barrier properties.

The silicon oxide film having 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. If 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 it is not preferable because the gas barrier property cannot be improved. On the other hand, if the thickness of the silicon oxide film exceeds 300 nm, cracks are easily formed, transparency and appearance are reduced, curling of the film is increased, and it is difficult to mass-produce, and productivity is reduced and cost is reduced. Increases, and disadvantages such as increase in the likelihood are likely to occur.

When the gas barrier film of the present invention is used for applications requiring flexibility, such as packaging materials, the thickness of the silicon oxide film to be formed should be 5 to 5 in consideration of the mechanical properties and applications of the silicon oxide film to be formed. 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 thicker than the above-described range of 5 to 30 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 becomes possible to make the gas barrier film thinner than a conventional product having the same gas barrier properties.

The silicon oxide film of the present invention is not particularly limited on one or both surfaces of the above-mentioned substrate,
It is preferably formed by 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 is performed at a low temperature (about -10 to 20) that does not cause thermal damage to the polymer resin.
There is an advantage that a desired material can be formed at a temperature of about 0 ° 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 organic silicon compound gas and an oxygen gas at a predetermined flow rate into a reaction chamber of a plasma CVD apparatus, and supplies DC power or a low-frequency to high-frequency voltage to the 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 invention, the silicon oxide film is transparent. However, in order to provide various uses, it is possible to arbitrarily laminate a layer having poor transparency among the base material and other laminated materials. 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 invention is used as a packaging material, it may be printed with colored ink or the like to provide a light-shielding property in order to protect the contents from light rays. 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, gas barrier film for film liquid crystal display, film organic E
When used in applications such as gas barrier films for L displays or gas solar cells, transparency of the gas barrier film as a whole is required, and the effect of the transparency of the silicon oxide film in the present invention is significant.

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 silicon oxide film having the above-mentioned barrier properties, and 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-mentioned resins, a resin composition comprising an acrylate compound having a radically reactive unsaturated compound, a resin composition comprising the above 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 manufactured 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.

Further, the substrate 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. Manufacturing Method The gas barrier film of the present invention can be manufactured by various manufacturing methods, and among them, it is preferable to form a film by a plasma CVD method.

As the preferable film forming conditions of the plasma CVD method, first, the temperature of the substrate at the time of film forming is -20 to 100.
° C, preferably within the range of -10 to 30 ° C.

Next, when the organic silicon compound gas and the gas containing oxygen atoms are used as the raw material gas, and the flow rate ratio between the organic silicon compound gas and the gas containing oxygen atoms is 1 when the organic silicon compound gas is 1, Within the range of 10 to 10, preferably 0 to
5 is set.

The effect can be further enhanced by increasing the input power per unit area in the plasma generating means of the plasma CVD apparatus or forming a space for confining the 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 Silazane, trimethoxysilane and the like can be preferably used, and one or more conventionally known ones such as tetramethyldisiloxane and normal methyltrimethoxysilane can be used.

However, in the present invention, Si-
Since it is necessary to include a certain amount of CH ₃ bond,
In particular, an organic silicon compound having a carbon-silicon bond in the molecule to some extent is preferably used. Specific examples include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), methyltrimethoxysilane, dimethylmethoxysilane, and the like. HMDSO) and methyltrimethoxysilane are preferably used.

As a gas containing an oxygen atom, 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 a 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 the plasma generation By setting the input power in the means within the above-described range, a gas barrier film having better gas barrier properties and excellent bending resistance and impact resistance can be obtained by using an organic compound having a carbon-silicon bond. The Si-C
An H ₃ bond is introduced. This is presumably because a crystal structure that is dense and has some flexibility is obtained.

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.

Further, the gas barrier film of the present invention comprises
A sample having a width of 100 mm is sandwiched between chucks with a length of 100 mm, and is stretched to 8% at an extension rate of 15 mm / min. In this state, the sample is held for 10 seconds. / M ² / day or less and a water vapor permeability of 0.5 g / m ² / day or less.

Since the gas barrier film of the present invention hardly permeates oxygen and water vapor which cause the quality of the contents to change, it can be used in applications where high gas barrier properties are required.
For example, it can be preferably used for packaging materials such as foods and pharmaceuticals and packaging materials for electronic devices and the like. Also,
Because of its high gas barrier properties, it has processing resistance, and 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 first embodiment, a heat sealing resin layer is laminated on the gas barrier film,
A second embodiment in which a conductive layer is laminated and a second embodiment will be described below.

1. First Embodiment (Laminated Material) FIG. 2 is a schematic sectional view showing a first embodiment of the present invention. In FIG. 2, 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.

The anchor coating agent layer 12 constituting the laminated material 11 uses, 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. 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.

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 the heat-sealing resin layer 13 is 5 to 300 μm, preferably 10 to 100 μm.
Can be set within the range.

FIG. 3 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-sealable 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 this 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 gas barrier film 1 because the gas barrier film 1 constituting the laminated material 21 has excellent transparency.

Further, in the present 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 this 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. 4 is a schematic sectional view showing another example of the laminated material of this embodiment. In FIG.
Is a gas barrier film 1 provided with 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 32. The resin layer 33, the base layer 34 provided on the other surface (the surface on which the vapor deposition layer is not formed) of the base 2 of the gas barrier film 1, and the heat-sealing resin layer 35 formed on the base layer 34 Have.

The anchor coating agent layer, the adhesive layer 32 and the heat-sealable 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 of 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 the present 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 laminated material in this embodiment, such as the laminated materials 11, 21 and 31 described above, can be formed by laminating a usual packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, or an extrusion method. 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 can be subjected to a pretreatment such as a corona treatment and an ozone treatment, if necessary. Further, for example, an isocyanate-based (urethane-based) or polyethyleneimine-based film can be used. 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 first embodiment.

Specifically, when the packaging container is a soft packaging bag, the heat-sealing resin layer of the laminated material of the first 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. 5 is a perspective view showing an example of such a packaging container. In FIG. 5, 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 can be, for example, a self-supporting packaging bag (standing pouch) or the like. Further, a tube container or the like can 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 spout, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

In the case where 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 paper substrates are laminated. 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 circular or other cylindrical paper can, and the like.

FIG. 6 is a perspective view showing an example of the above-mentioned liquid-filled paper container which is a packaging container of the present invention.
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. 4, and includes pressing lines m, m,... For bending in forming the 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 drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and the like. Things.

2. Second Embodiment (Laminated Material) A second 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.
1 illustrates 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. 8, between the vapor deposition film 3 and the base material 2, the vapor deposition film 3
May be formed with an anchor coat agent layer 42 for improving the adhesiveness. 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.

The thickness of the conductive layer 41 varies greatly depending on the composition, the application and the like.
It is formed within a range of 200 nm.

The conductive layer 41 has a resistance 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 more or a urethane acrylate prepolymer having a melting point of 50 ° C. or more 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 second 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.

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.

[0100]

The present invention will be described more specifically with reference to the following examples and comparative examples.

(Example 1) As shown in FIG.
As a sheet-shaped (30 cm × 21 cm) biaxially stretched polyamide film (manufactured by Toyobo Co., Ltd., N1102, thickness 1)
5 μm) was prepared and mounted on the lower electrode 114 side in the chamber 102 of the plasma CVD apparatus 101. Next, C
In the chamber 102 of the VD device 101, the ultimate vacuum degree is 3.0 × 1 by an oil rotary pump and a turbo molecular pump.
The pressure was reduced to 0 ⁻⁵ Torr (4.0 × 10 ⁻³ Pa). Further, as a raw material gas 112, hexamethyldisiloxane (HMDSO) gas (Dow Corning Silicone Toray Co., Ltd., SH200, 0.65CSt) and oxygen gas (Taiyo Toyo Oxygen Co., Ltd., purity 99.9999% or more) ) Was prepared.

Next, power having a frequency of 90 kHz (input power: 300 W) was applied to the lower electrode 114. Then, an HMDSO gas of 1 sccm, an oxygen gas of 5 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 the gas barrier film of Example 1 was obtained.

(Example 2) Organic silicon gas (HMDSO)
A gas barrier film of Example 2 was obtained in the same manner as in Example 1 except that the flow rate, oxygen gas flow rate, and input power of were changed as described in the table below.

(Comparative Examples 1 to 7) Organic silicon gas (HMDS)
The gas barrier films of Comparative Examples 1 to 7 were obtained in the same manner as in Example 1 except that the flow rate of O), the oxygen gas flow rate, and the input power were changed as described in the table below.

(Evaluation Method) The gas barrier films of Examples 1 and 2 and Comparative Examples 1 to 7 were evaluated by the following evaluation methods.

1. Measurement of Component Ratio The components of the silicon oxide film are ESCA (VG Science, UK)
ntic, ESCA LAB220i-XL)
Was measured by Ag-3d-5 /
Monochrome A with 2-peak intensity, 300K-1 Mcps
An X-ray source and a slit having a diameter of about 1 mmφ were 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 the measurement was performed using software Eclipse version 2.1 (VG Sc, UK) attached to the above ESCA device.
Sientis 2p, C: 1
s, O: binding energy of 1 s (Bindi
ng Energy). At this time, Shirley background removal was performed for each peak, and the sensitivity coefficient of each element was corrected for the peak area (for C = 1, Si = 0.817, O = 2.93).
0) was performed to determine the atomic ratio. Regarding the obtained atomic number ratio, the number of Si atoms was set to 100, and the other components O and C
Was calculated and evaluated as a component ratio.

2. IR Measurement IR measurement is performed using a Fourier transform infrared spectrophotometer (Herchel FT / I, manufactured by JASCO) equipped with an ATR (multiple reflection) measurement device (ATR-300 / H, manufactured by JASCO).
R-610). The infrared absorption spectrum was obtained by using a germanium crystal as the prism, and making the incident angle 4
Measured at 5 degrees.

3. Measurement of Refractive Index The refractive index of the silicon oxide film can be measured using an optical spectrometer (manufactured by Shimadzu Corporation,
V-3100PC). From the measurement results of the obtained transmittance and reflectance, 633 was obtained by using the optical interference method.
It was evaluated by the refractive index in nm.

4. Tensile test A sample having a width of 100 mm was sandwiched between chucks with a chuck interval of 100 mm, and the chuck interval was increased at a speed of 15 mm / min. Chuck spacing of 2%, 5%, and 8
%, Each was held in that state for 10 seconds and then subjected to a gas permeability test.

5. Impact resistance test Impact resistance test using a DuPont impact tester (JIS-K-5400.6.13
It was carried out based on B). After dropping with a weight load of 100 g, the sample was observed under a microscope at a magnification of 1000 times, and the drop distance at which no crack was observed was measured.

6. Gas permeation test The oxygen gas permeability was measured using an oxygen gas permeability measuring device (MOCO
N Company, OX-TRAN 2/20), 23 ° C,
It was measured under dry (0% Rh) conditions. The water vapor transmission rate can be measured using a water vapor transmission rate measuring device (PERM, manufactured by MOCON).
ATRAN-W3 / 31), 37.8 ° C, 100
% Rh was measured.

The results are summarized in the following table. Table 1 summarizes the film forming conditions, and Table 2 summarizes the evaluation results.

[0113]

[Table 1]

[0114]

[Table 2]

As shown in Comparative Examples 1 to 3, in the state where no tension is applied, the smaller the carbon content, the better the gas barrier properties. However, these have low gas barrier properties after tensile and poor impact resistance. In order to improve these characteristics, it is better to increase the amount of Si—CH ₃ (Example 1).
~ 2, Comparative Examples 4, 6-7). On the other hand, if the amount of carbon is too large, a carbon film is formed, the film becomes hard due to CC bond, and the gas barrier property after tension is reduced (Comparative Example 5). The density of the film cannot be determined only by the refractive index (the refractive index increases as the carbon content increases).
i, the component ratio of O and C, Si-O-Si initial gas barrier property by controlling the limiting and Si-CH ₃ content within a predetermined range of peak positions is also good and better gas barrier properties after pulling Thus, a gas barrier film having further impact resistance can be obtained (Examples 1 and 2).

[0116]

As described above, according to the present invention,
Component Ratio of Silicon Oxide Film Acting as Gas Barrier Film and I
By controlling the characteristic consisting of R absorption within the above range, it is possible to obtain a gas barrier film having extremely excellent gas barrier properties and a gas barrier film having excellent bending resistance and impact resistance. it can. Therefore, it can be preferably used for applications requiring high gas barrier properties even after processing, for example, 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 sectional view showing an example of a laminated material (first embodiment) using the gas barrier film of the present invention.

FIG. 3 is a schematic sectional view showing another example of a laminated material (first embodiment) using the gas barrier film of the present invention.

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

FIG. 5 is a schematic plan view showing an example of a packaging container using the gas barrier film of the present invention.

FIG. 6 is a schematic perspective view showing another example of a packaging container using the gas barrier film of the present invention.

FIG. 7 is a plan view of a blank plate used for manufacturing the packaging container shown in FIG.

FIG. 8 is a schematic cross-sectional view showing one example of a laminated material (second embodiment) using the gas barrier film of the present invention.

FIG. 9 is a configuration diagram illustrating an example of a plasma CVD apparatus.

[Explanation of symbols]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 16/40 C23C 16/40 F term (Reference) 3E086 AB01 AD01 AD02 BA04 BA12 BA15 BB02 BB05 CA01 CA28 CA31 4F100 AA20B AT00A BA02 BA03 BA04 BA10A BA10B BA10C BA10D EH66B GB16 GB41 JD02B JG01D JK10 JL13C JN18B YY00B 4K030 BA44 CA07 CA12 DA08 FA03 JA01 LA01 LA11

Claims (8)

[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 in the range of 180 to 200 O atoms to 100 Si atoms, and has a Si atom number of 100. And a component ratio of 40 to 80 C atoms, and Si—O between 1045 and 1060 cm ⁻¹
-Si absorption due to stretching vibration and 1274
A gas barrier film having IR absorption at ± 4 cm ^{−1 based} on Si—CH ₃ stretching vibration. 2. The gas barrier film according to claim 1, wherein the silicon oxide film has a refractive index of 1.50 or more and 1.70 or less. 3. The oxygen transmission rate is 0.5 cc / m ² / day.
The gas barrier film according to claim 1, wherein the water vapor transmission rate is 0.5 g / m ² / day or less. 4. The silicon oxide film has a thickness of 5 to 300 n.
The gas barrier film according to claim 1, wherein m is m. 5. 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 4. 6. A packaging container obtained by using the laminated material according to claim 5 to form a bag or a box by heat-sealing the heat-sealing resin layer. 7. A laminated material, characterized in that a conductive layer is formed on at least one surface of the gas barrier film according to any one of claims 1 to 4. 8. An image display medium comprising the laminate according to claim 7 as a substrate, and an image display layer formed on the conductive layer.