JP2001353807A - Film with barrier properties and laminate material using the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film with gas barrier properties which shows outstanding barrier properties for inhibiting the permeation of an oxygen gas, water vapor and the like and further, superb flexing properties with a remarkable suitability for working steps such as printing, laminating, bag making and the other after- treatments and is useful for packaging drinks, drugs, cosmetics, chemicals, electronic parts and the other various kinds of articles as fillings as well as a laminate material using the film with barrier properties. SOLUTION: An inorganic oxide-vapor deposited film by a chemical vapor growth process is formed on one of the sides of a base film and further, a plasma treated area is formed on the surface of the inorganic oxide-vapor deposited film. Next, a primer layer is formed on the plasma treated area. Also the laminate material using the film with barrier properties is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a barrier film and a laminated material using the same. For example, it has excellent suitability for post-processing such as printing, laminating, bag making, etc. The present invention relates to a barrier film useful for filling and packaging an article of the present invention and a laminated material using the same.

[0002]

2. Description of the Related Art Conventionally, various packing materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, and others. Among them, in recent years,
As a barrier material to prevent the permeation of oxygen gas or water vapor, a monomer gas composition for vapor deposition composed of an organosilicon compound, oxygen gas, inert gas, and others is used on one surface of a plastic substrate. In addition, a transparent gas barrier film in which a deposited film of an inorganic oxide such as silicon oxide is formed by using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method has attracted attention. Thus, the above-mentioned transparent gas barrier film is produced on one side, or on both sides, by laminating another plastic film, a paper base material, etc., to produce a laminated material having various layer constitutions,
Using the laminated material, it is made into a bag or box making to produce packaging containers of various forms, after which, in the packaging container, for example, food and drink, pharmaceuticals, cosmetics, etc. The company manufactures packaged products by filling and packaging various articles and supplies them to the market. The above packaging products have a high barrier property of preventing permeation of oxygen gas or water vapor, and are excellent in storage of contents, storage stability, quality assurance, etc.,
After use, compared to conventional packaging containers that use barrier materials such as aluminum foil or polyvinylidene chloride-based resin film, it is more suitable for disposal of packaging containers, etc. , Its development, demand, etc. are expected.

[0003]

However, in the above-mentioned transparent gas barrier film, since a monomer gas for vapor deposition such as an organic silicon compound is used, a carbon component or the like is contained in the vapor deposited film. Further, the value of X is unstable in the composition of a deposited film of an inorganic oxide such as silicon oxide represented by the general formula SiO _X. For this reason,
For example, on the inorganic oxide vapor deposition film, printing processing to form a printed pattern or the like, or control of the uniformization of the vapor deposition film surface which has an effect when performing lamination processing or the like for laminating a plastic film or the like, Alternatively, there is a problem that control such as optimization is extremely difficult. Further, in the above transparent gas barrier film, since a carbon component or the like is contained in the deposited film, the wettability of the surface is poor, and printing processing, lack of post-processing suitability such as lamination processing, for example, There is a problem in that poor printing, delamination (delamination) and the like are induced, and productivity and the like of a laminated material or the like as a packaging material are significantly reduced. In order to solve the above-mentioned problems, for example, in order to improve the tight adhesion between the plastic substrate and the inorganic oxide deposited film, the surface of the plastic substrate is subjected to plasma treatment or the like, and a polar group or the like is applied. Has been attempted to improve the surface activity and the like, form a vapor-deposited film of an inorganic oxide on the surface to produce a transparent gas barrier film, and improve its printability, close adhesion and the like. Depending on the plasma treatment conditions, polymer chains and the like on the surface of the plastic substrate are destroyed and the molecular weight is reduced, thereby causing cohesive failure on the surface of the plastic substrate where the inorganic oxide vapor-deposited film is tightly adhered. Etc. are derived, and as a result,
In this case, there is a problem that the strength and the bending resistance are lowered. Attempts have also been made to perform the plasma treatment offline and then form an inorganic oxide deposited film. However, once the plasma-treated plastic substrate is exposed to the atmosphere once, the plastic substrate is exposed. There is a problem in that foreign substances such as moisture are contaminated on the plasma-treated surface of the material, and it is extremely difficult to achieve the desired effect, and the material is unstable. Therefore, the present invention is excellent in transparency, barrier properties for preventing permeation of oxygen gas and water vapor and the like, and further,
Excellent flexibility, for example, printing, laminating,
Barrier film having excellent suitability for post-processing such as bag making and other, and useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic components, etc. Is to provide a laminated material using the same.

[0004]

As a result of various studies to solve the above-mentioned problems, the present inventor has found that before providing an inorganic oxide vapor-deposited film on one surface of a substrate film, ,
Providing a surface pretreatment layer, and then on the surface of the surface pretreatment layer,
A plasma-enhanced chemical vapor deposition method is used to provide a vapor-deposited film of an inorganic oxide such as silicon oxide. Further, a plasma-treated surface is provided in-line on the surface of the vapor-deposited film of the inorganic oxide. When a barrier film was manufactured by providing a primer-agent layer, on one surface of the base film,
Since a dense inorganic oxide vapor-deposited film is formed via the surface pretreatment layer, excellent adhesion between the substrate film and the inorganic oxide vapor-deposited film is excellent, and the surface of the inorganic oxide vapor-deposited film is also excellent. To
Since the primer agent layer is provided via the plasma-treated surface, excellent adhesion between the inorganic oxide vapor-deposited film and the primer agent layer, excellent bending resistance, etc., printing, laminating, etc. There are no problems such as printing defects, lamination defects, and other defects in post-processing such as processing, bag making, and other processing. In addition, cracks and the like are observed in the inorganic oxide deposited film. It has an extremely high barrier property against oxygen gas or water vapor and has excellent transparency, and is useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic parts, etc. It has been found that a novel barrier film and a laminated material using the same can be produced, and the present invention has been completed.

That is, according to the present invention, a vapor-deposited inorganic oxide film is formed on one surface of a substrate film by a chemical vapor deposition method, and a plasma-treated surface is further formed on the surface of the vapor-deposited inorganic oxide film. And then, on the plasma processing surface, a primer
TECHNICAL FIELD The present invention relates to a barrier film provided with an agent layer and a laminate using the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the layer structure and the like of the barrier film and the laminate according to the present invention will be described with reference to the drawings. FIGS. 1 and 2 are schematic diagrams showing an example of the layer structure of the barrier film according to the present invention. FIG. 3 is a schematic sectional view showing an example of a layer configuration of a laminated material manufactured using the barrier film shown in FIG.

In the barrier film A according to the present invention, as shown in FIG. 1, a vapor-deposited film 2 of an inorganic oxide is provided on one surface of a base film 1 by a chemical vapor deposition method. The basic structure is such that a plasma treated surface 3 is provided on the surface of the oxide deposited film 2 and then a primer agent layer 4 is provided on the plasma treated surface 3. As another example of the barrier film according to the present invention, as shown in FIG. 2, before providing the inorganic oxide vapor-deposited film 2 on one surface of the base film 1,
A surface pre-treatment layer 5 is provided, and then, on the surface pre-treatment layer 5, an inorganic oxide deposited film 2 is formed by chemical vapor deposition in the same manner as described above. the second surface, the provided plasma-treated surface 3, then the on the plasma treated surface 3, primer - adhesive layer 4 text be exemplified barrier film a ₁ according to the present invention having the configuration in which the You. Thus, as an example of a laminate manufactured using the barrier film according to the present invention, as shown in FIG. 3, as shown in FIG. 3, the barrier film A according to the present invention shown in FIG. For example, an inorganic oxide vapor-deposited film 2 formed by a chemical vapor deposition method is provided on one surface of a base film 1, and the surface of the inorganic oxide vapor-deposited film 2 is further subjected to plasma treatment. A surface 3 is provided, and then a primer material layer 4 is provided on the plasma-treated surface 3. The laminated material B according to the present invention having a configuration in which the resin layer 6 is provided can be exemplified. Of course, in the present invention, the barrier film B shown in FIG.
In the same manner as described above, the laminated material according to the present invention can be produced. The above examples illustrate one or two examples of the barrier film according to the present invention and a laminate using the same.
Of course, the present invention is not limited by this. For example, although not shown in the above-described barrier films and laminated materials shown in FIGS. 1 and 2, the inorganic oxide vapor-deposited film may be composed of not only one layer but also a multilayer film composed of two or more layers. Although not shown, in the laminated material shown in FIG. 3 described above, depending on its packaging purpose, the contents to be filled and packed, the distribution form, and the like, another base material or the like is further arbitrarily added and laminated. Is what you can do.

Next, in the present invention, the materials constituting the barrier film, the laminated material and the like according to the present invention, the production method and the like will be described in more detail. First, the barrier film and the laminated material according to the present invention are formed As a base film to be used, it has excellent chemical or physical strength, withstands the conditions for forming a vapor-deposited film of an inorganic oxide described below, etc., and without impairing the properties of the vapor-deposited film of the inorganic oxide, etc. Substrates that can be held can be used. In the present invention, specifically, as the base film, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin) ), Acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, etc. Polyamide resin such as nylon,
Films or sheets of various resins such as a polyurethane resin, an acetal resin, a cellulose resin, and others can be used. In the present invention, among the above resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, and the cutting method are used. A method of forming the above various resins alone using a film forming method such as an inflation method, an inflation method, or the like, or a multi-layer coextrusion film forming using two or more kinds of resins. A film or a sheet of various resins is manufactured by a method of forming two or more resins, and a method of mixing and forming a film before forming a film. For example, various resin films or sheets stretched in a uniaxial or biaxial direction using a tenter method or a tuber method can be used. In the present invention, the film thickness of various resin films or sheets is 6 to 200 μm.
And more preferably about 9 to 100 μm.

[0010] One or more of the above various resins are used, and when forming the film, for example, the processability, heat resistance, weather resistance, mechanical properties, dimensional stability,
For the purpose of improving or modifying the antioxidant properties, slip properties, mold release properties, flame retardancy, anti-mold properties, electrical properties, strength, etc., various plastic additives and additives can be added. Can,
The addition amount can be arbitrarily added from a very small amount to several tens% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
An antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used, and further, a modifying resin and the like can be used.

In the present invention, the surface of the film or sheet of various resins may be optionally used to improve the tight adhesion with a later-described inorganic oxide vapor-deposited film.
A desired surface pretreatment layer can be provided in advance. In the present invention, as the surface pretreatment layer,
For example, a corona discharge treatment, an ozone treatment, a low-temperature plasma treatment using an oxygen gas or a nitrogen gas, a glow discharge treatment, an oxidation treatment using a chemical agent or the like, an optional treatment such as a pretreatment, etc. A corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided. The above-mentioned surface pretreatment is carried out as a method for improving the tight adhesion between various resin films or sheets and a later-described inorganic oxide vapor-deposited film. As a way to improve
In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a vapor-deposited film may be formed on the surface of a film or sheet of various resins. An anchor coating agent layer or the like can be optionally formed to form a surface pretreatment layer. As the coating agent layer of the above pretreatment, for example, polyester-based resin, polyamide-based resin,
Polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin,
A resin composition containing, as a main component of the vehicle, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

In the present invention, the above-mentioned surface pretreatment layer is preferably formed by applying a surface pretreatment such as a corona discharge treatment, a plasma treatment, or a flame treatment. Layers are preferred. Thus, in the present invention, the surface pretreatment layer can be provided in advance on one surface of the substrate film before the inorganic oxide vapor deposition film is provided. That is, in the present invention, it is usually preferable to provide a surface pretreatment layer on one surface of the base film in advance, and then provide a vapor-deposited film of an inorganic oxide on the surface pretreatment layer. Things. However, on one surface of the base film, a surface pretreatment layer such as a corona discharge treatment layer is provided in advance, and this is, for example, unwound in a vacuum such as a plasma enhanced chemical vapor deposition apparatus, or when wound up. On the other hand, if the degree of corona discharge treatment is too large, there is a problem that the surface free energy of the base film is large, so that a blocking phenomenon or the like occurs, which significantly impairs the mechanical suitability and the like. Therefore, in the present invention, for the surface pretreatment layer such as the corona discharge treatment layer, the static and kinetic friction coefficients are 0.4 μ to
It is preferable to adjust the degree of treatment to about 0.7 μm, preferably about 0.5 μm to 0.7 μm. In the above, the coefficient of static and kinetic friction is 0.4 μm,
If less than μ, it is not preferable because there is a problem of poor wettability.
If it exceeds, it is not preferable because a blocking phenomenon or the like occurs.

Next, in the present invention, the vapor-deposited inorganic oxide film constituting the barrier film, the laminated material and the like according to the present invention will be described. It can be formed by a chemical vapor deposition method (Ch) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method.
electrical Vapor Deposition method,
A deposited film of an inorganic oxide can be formed by using a method such as a CVD method. More specifically, on one side of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, and an inert gas such as an argon gas and a helium gas is used as a carrier gas. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed by using a low-temperature plasma-enhanced chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and a low-temperature plasma generator or the like. In the above, as the low-temperature plasma generator, for example, a generator such as a high-frequency plasma, a pulse wave plasma, or a microwave plasma can be used. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a generator using a high-frequency plasma method.

Specifically, a method of forming a deposited film of an inorganic oxide by the low-temperature plasma enhanced chemical vapor deposition method will be described by way of example. FIG. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic configuration diagram of a low-temperature plasma-enhanced chemical vapor deposition apparatus showing an outline of a method for forming a deposited oxide film. As shown in FIG. 4 described above, in the present invention, the base film 1 is unwound from an unwinding roll 13 disposed in a winding chamber 12 of a plasma enhanced chemical vapor deposition apparatus 11, and The material film 1 is conveyed at a predetermined speed through the auxiliary roll 14 onto the cooling / electrode drum 15 in the chamber 12. In the present invention, oxygen gas, an inert gas, a monomer gas for vapor deposition such as an organic silicon compound, and the like are supplied from the gas supply devices 16 and 17 and the raw material volatile supply device 18 and the like. While adjusting the mixed gas composition for vapor deposition, the mixed gas composition for vapor deposition was introduced into the chamber 12 through the raw material supply nozzle 19, and the base material conveyed onto the peripheral surface of the cooling / electrode drum 15 was obtained. Plasma is generated by the glow discharge plasma 20 on the material film 1 and is irradiated with the plasma to form a deposited film of an inorganic oxide such as silicon oxide, thereby forming a film. In the present invention, at that time,
A predetermined power is applied to the electrode drum 15 from a power source 21 disposed outside the chamber 12, and a magnet 22 is disposed near the cooling / electrode drum 15 to promote generation of plasma. Then, the base film 1 on which the deposited film of the inorganic oxide such as silicon oxide is formed is wound up on a take-up roll 24 via an auxiliary roll 23 or the like, and the inorganic oxide It can form a deposited film. In the figure, reference numeral 25 denotes a vacuum pump. The above exemplification is merely an example, and it goes without saying that the present invention is not limited thereby. Although not shown, in the present invention, the continuous film of the inorganic oxide is not limited to one layer of the continuous film of the inorganic oxide, but may be a multilayer film in which two or more layers are stacked. The materials may be used alone or as a mixture of two or more kinds, and a continuous film of an inorganic oxide mixed with different materials may be formed.

In the above, the inside of the winding chamber 12 is depressurized by the vacuum pump 25, and the degree of vacuum is 1 × 10 ^-1 to 1
× 10 ⁻⁸ Torr, preferably a degree of vacuum of 1 × 10 ⁻³ to
It is desirable to adjust to about 1 × 10 ⁻⁷ Torr. Further, in the raw material volatilization supply device 18, the organic silicon compound as the raw material is volatilized, and the gas supply devices 16, 1
Mixed with oxygen gas, inert gas, etc. supplied from 7,
This mixed gas is supplied to a chamber through a raw material supply nozzle 19.
12 is introduced. In this case, the content of the organic silicon compound in the mixed gas is about 1 to 40%, the content of the oxygen gas is about 10 to 70%, and the content of the inert gas is
For example, the mixing ratio of the organic silicon compound, the oxygen gas, and the inert gas is set to 1: 10%.
6: 5 to 1:17:14. On the other hand, since a predetermined voltage is applied to the cooling / electrode drum 15 from the power supply 21, the glow discharge plasma 20 near the opening of the raw material supply nozzle 19 and the cooling / electrode drum 15 in the chamber 12. Is generated, and the glow discharge plasma 20 is derived from one or more gas components in the mixed gas. In this state, the base film 1 is transported at a constant speed, and the glow discharge plasma 20 The substrate film 1 on the peripheral surface of the cooling / electrode drum 15
On which an evaporated film of an inorganic oxide such as silicon oxide can be formed. At this time, the degree of vacuum in the take-up chamber 12 is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ To.
rr position, preferably a degree of vacuum of 1 × 10 ^-1 to 1 × 10 ^-2 T
It is desirable to adjust to the orr level, and it is desirable to adjust the transport speed of the base film 1 to about 10 to 300 m / min, preferably to about 50 to 150 m / min.

The above-mentioned plasma chemical vapor deposition apparatus 1
In 1, the vapor-deposited film of an inorganic oxide such as silicon oxide is formed on the base film 1 in the form of a thin film in the form of SiO _X while oxidizing a plasma-converted raw material gas with oxygen gas. The formed deposited film of an inorganic oxide such as silicon oxide is a continuous layer that is dense, has few gaps, and is highly flexible. The property is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. Further, in the present invention, Si
O _X plasma by the substrate film 1 of the surface, is cleaned, the surface of the substrate film 1, a polar group and pretend - since radicals such as occurs, vapor deposited film of an inorganic oxide such as silicon oxide is formed and This has the advantage that the close adhesion to the base film is high. Further, as described above, the degree of vacuum at the time of forming a deposited film of an inorganic oxide such as silicon oxide is 1
× 10 ^-1 to 1 × 10 ^-4 Torr, preferably 1 × 1
Since the pressure is adjusted to about 0 ^-1 to 1 × 10 ^-2 Torr, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by a conventional vacuum deposition method is 1 × 10 ^-4 to 1 × 10 Torr. ^-5 Torr
Base film 1
The time required for setting a vacuum state when exchanging a raw material can be shortened, the degree of vacuum is easily stabilized, and the film forming process is stabilized.

In the present invention, a deposited silicon oxide film formed by using a vaporized monomer gas such as an organic silicon compound is chemically reacted with a vaporized monomer gas such as an organic silicon compound and oxygen gas. the reaction product is closely deposited on one surface of a substrate film, dense, and forms a thin film rich in flexibility or the like, usually, the general formula SiO _X (provided that, X
Is a continuous thin film mainly composed of silicon oxide represented by the following formula: Thus, from the viewpoints of transparency, barrier properties, and the like, the silicon oxide deposited film represented by the general formula Si
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of a continuous film of silicon oxide represented by. In the above, the value of X changes depending on the molar ratio of the vaporized monomer gas to oxygen gas, the energy of the plasma, and the like. Generally, the gas permeability decreases as the value of X decreases, but the film itself does not. Is yellowish,
Transparency worsens.

The above-mentioned silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of one or more of carbon, hydrogen, silicon or oxygen. It is characterized by comprising a continuous film containing the types by chemical bonding or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in a graphite-like, diamond-like, fullerene-like, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained due to chemical bonding or the like. To give a specific example, CH
Hydrocarbon with _three sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl derivative such as SiH ₂ OH silanol. In addition to the above, by changing the conditions and the like of the vapor deposition process, the type, amount, and the like of the compound contained in the vapor-deposited silicon oxide film can be changed. The content of the above compound in the silicon oxide vapor deposition film is 0.1 to 50.
%, Preferably about 5 to 20%. In the above, if the content is less than 0.1%,
Impact resistance, spreadability, flexibility, etc. of the deposited film of silicon oxide become insufficient, and due to bending, scratches, cracks, etc. are easily generated, and it becomes difficult to stably maintain high barrier properties, On the other hand, if it exceeds 50%, the barrier properties are undesirably reduced. Furthermore, in the present invention, the content of the above compound in the silicon oxide vapor deposition film is preferably reduced in the depth direction from the surface of the silicon oxide vapor deposition film, whereby the silicon oxide vapor deposition film is formed. On the surface of the above, the impact resistance and the like can be enhanced by the above-mentioned compounds and the like. Has the advantage that the tight adhesion of the sapphire becomes strong.

Thus, in the present invention, the above-mentioned deposited film of silicon oxide may be, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec.)
onion Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of a deposited silicon oxide film using a method of performing analysis by ion etching in the depth direction or the like using a surface analysis device such as O.I. can do. In the present invention, the thickness of the deposited silicon oxide film is preferably about 50 to 4000 °, and specifically, about 100 to 1000 °. Then, in the above, 1000 °, furthermore, 40
When the thickness is more than 00 °, cracks and the like are easily generated in the film, which is not preferable.
When the angle is less than 0 °, it is not preferable because it is difficult to exhibit the barrier effect. In the above description, the film thickness can be measured, for example, by a fundamental parameter method using a fluorescent X-ray analyzer (model name: RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as means for changing the thickness of the deposited film of silicon oxide, increasing the volume velocity of the deposited film, that is, a method of increasing the amount of the monomer gas and the oxygen gas or the rate of the deposition. It can be performed by a method of slowing down.

Next, in the above, as a monomer gas for vapor deposition of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used. In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is advantageous in terms of handleability and formed deposited film. It is a particularly preferable raw material in view of its characteristics and the like. In the above, for example, an argon gas, a helium gas, or the like can be used as the inert gas.

Next, in the present invention, the plasma treated surface constituting the barrier film, laminated material, etc. according to the present invention will be described. As the plasma treated surface, a plasma generated by ionizing a gas by glow discharge is used. The plasma-treated surface can be formed by using a plasma surface treatment method for performing surface modification using a gas. That is, in the present invention, oxygen gas,
The plasma processing surface can be formed by performing plasma processing by using one or more inorganic gases such as nitrogen gas, argon gas, and helium gas as the plasma gas. Therefore, in the present invention, it is preferable that the plasma treatment is performed by using an oxygen gas or a mixed gas of an oxygen gas and an argon gas during the plasma discharge treatment. By such a plasma treatment, it is possible to perform the plasma treatment at a lower voltage, whereby a plasma treatment surface can be favorably provided on the surface of the inorganic oxide deposition film.

In the present invention, as the plasma treatment, an oxygen gas or a mixed gas of an oxygen gas and an argon gas is used, and a vapor-deposited inorganic oxide film is formed on the surface of the substrate film. It is desirable to perform the process in-line immediately after the formation. That is, in the present invention, as shown in FIG. 4 described above, the base film 1 on which the inorganic oxide vapor-deposited film is formed is guided to the auxiliary roll 23 through the cooling / electrode drum 15 peripheral surface. Immediately before, a plasma processing device 26 is provided as a pre-processing unit, and the plasma processing device 26 allows the plasma processing device 26 to inline the surface of the deposited inorganic oxide film formed on the base film 1. By sufficiently performing the plasma processing, the plasma processing surface according to the present invention can be formed. Thus, in the present invention, by the plasma treatment as described above, contaminants and the like due to moisture adsorption on the surface of the deposited film of the inorganic oxide are minimized, the reaction of unreacted substances on the surface is promoted, and In addition, impurities such as carbon components, dust, etc. are removed, and the film composition of the surface of the deposited inorganic oxide film is made uniform, and the wettability and the like are improved. In the present invention, by forming the plasma-treated surface as described above, a coating process such as a primer or an adhesive, a printing process for forming a printed pattern, etc. on the inorganic oxide vapor-deposited film, Laminating process for laminating base materials such as other plastic films, etc., and other post-processing processes. It is capable of producing a barrier material excellent in properties, productivity, running cost properties, etc., and excellent in oxygen gas barrier properties, water vapor barrier properties, and the like.

In the present invention, even if a primer agent or the like described below is coated on the surface of the inorganic oxide vapor-deposited film by the above-described plasma treatment, the two are excellent in close adhesion. , As a result, excellent in bending resistance and the like, for example,
In post-processing such as film winding, printing, laminating, or bag making, the above-mentioned inorganic oxide vapor-deposited film can be prevented from generating cracks and the like. It also has the advantage that suitability can be improved. In the present invention, since the plasma treatment is performed in-line immediately after the formation of the inorganic oxide vapor-deposited film, the production cost is also reduced.
This is extremely superior to other methods.

In the present invention, in the above-mentioned plasma processing, the plasma processing conditions are extremely important, and the effects obtained by the conditions are completely different. Thus, in the present invention, the plasma processing conditions include plasma discharge power, glow discharge pressure, and the like. In the present invention, the plasma processing includes:
For example, the stronger the plasma treatment, the better the tight adhesion improves.
In the present invention, the plasma discharge power is about 40 W
· Min / m ² to 100 W · min / m ^2-position is the most preferred. In the present invention, the plasma power source may be AC or DC. Therefore, the glow discharge pressure is preferably about 0.5 to 5.0 × 10 ⁻² mbar. However, the low vacuum is not preferable because the effect of plasma on the base film is weakened.

In the present invention, in the plasma processing, a method of generating plasma includes, for example, a DC glow discharge, a high frequency (Audio Frequency).
ency: AF, Radio Frequency: R
F) It can be performed using three types of devices such as discharge and microwave discharge. In the present invention, the surface immediately after the formation of the inorganic oxide vapor-deposited film is subjected to the above-described plasma treatment by the plasma treatment surface described in VG, UK.
By performing elemental analysis on the treated surface using an X-ray photoelectron spectrometer (Model name, XPS) manufactured by Scientific, as described above, moisture and dust attached to the surface can be removed. A plasma-treated surface with a thin and highly smooth oxide film formed on the treated surface by oxygen molecules activated in the plasma causing a chemical reaction with the surface of the inorganic oxide deposited film. And, furthermore,
For example, it can be confirmed that the surface is a plasma treated surface on which a functional group such as an oxygen group is formed.

Next, in the present invention, a primer agent layer constituting a barrier film, a laminate or the like according to the present invention will be described. First, as the primer agent layer, first, a polyurethane-based resin is mainly used as a vehicle. As a component, 0.05 to 10% by weight, preferably 0.1 to 5% by weight, of the silane coupling agent is added to 1 to 30% by weight of the polyurethane resin. 0.1-20% by weight of filler, preferably 1-1
It is added at a ratio of about 0% by weight, and if necessary, additives such as a stabilizer, a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber, etc. are optionally added, and a solvent, a diluent, etc. are added. The polyurethane resin composition is prepared by mixing well. next,
In the present invention, the polyurethane resin composition prepared as described above is used and, for example, a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, and other coats are used. Using a coating method, a coating is performed on the above-described inorganic oxide vapor-deposited film, and then the coating film is dried to remove a solvent, a diluent, and the like. -A primer agent layer according to the present invention can be formed by performing jing processing or the like. In the present invention, the thickness of the primer agent layer of the polyurethane resin composition is, for example, 0.01 to 50 μm
And preferably about 0.1 to 5 μm.

In the above, as the polyurethane resin, for example, a polyurethane resin obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound can be used. Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate
Aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate, or polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate; Polyether polyol, polyester polyol
One- or two-part curable polyurethane resins obtained by reaction with a hydroxyl group-containing compound such as polyester, polyacrylate polyol or the like can be used. Thus, in the present invention, by using the polyurethane resin as described above, the elongation of the primer agent layer is improved, and for example, laminating processing or post-processing suitability such as bag making processing is improved. It is intended to prevent the occurrence of cracks and the like in the deposited film of the inorganic oxide during post-processing.

In the above description, as the silane coupling agent, an organic functional silane monomer having a binary reactivity can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrichlorosilane. Ethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltri Acetoxysilane, γ-mercaptopropyltrimethoxysilane, N-
β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyl One or more of triethoxysilane, an aqueous solution of γ-aminopropyl silicone and the like can be used. The silane coupling agent as described above,
A functional group at one end of the molecule, usually a chloro, alkoxy, or acetoxy group, etc. is hydrolyzed to form a silanol group (SiOH), which is a metal constituting a deposited film of an inorganic oxide, or An active group on the surface of the inorganic oxide film, for example, a functional group such as a hydroxyl group, by some action, for example, a reaction such as a dehydration condensation reaction occurs, silane coupling on the surface of the inorganic oxide film. The agent is modified by a covalent bond or the like, and a strong bond is formed on the surface of the deposited inorganic oxide film of the silanol group itself by adsorption or hydrogen bonding. On the other hand, the other end of the silane coupling agent vinyl, methacryloxy, amino, epoxy, or
An organic functional group such as mercapto is formed on a thin film of the silane coupling agent, for example, constituting a printing pattern layer, a laminating adhesive layer, an anchor coating agent layer, and other layers. Reacts with the material to form a strong bond,
The heat-sealing resin layer is firmly and tightly bonded via the above-mentioned printing pattern layer, laminating adhesive layer, anchor coating agent layer, etc., thereby increasing the laminating strength. Thus, in the present invention, a strong laminated structure having high laminate strength can be formed. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized, and the heat is applied through a vapor-deposited inorganic oxide film and a printed pattern layer, an adhesive layer or an anchor coating agent layer. The purpose is to improve the tight adhesion with the sealable resin layer, thereby increasing the laminate strength and the like.

Further, as described above, as the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. The above-mentioned filler adjusts the viscosity and the like of the polyurethane-based resin composition liquid, improves its coating suitability, and binds to the polyurethane-based resin as a binder resin via a silane coupling agent. And to improve the cohesive force of the coating film.

In the present invention, for example, a desired printed pattern composed of characters, figures, symbols, pictures, etc. can be formed on the primer agent layer formed above. . The printed pattern contains one or more of ordinary ink vehicles as main components, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent. , Optionally adding one or more of additives such as crosslinking agents, lubricants, antistatic agents, fillers, etc., and further adding colorants such as dyes and pigments,
The ink composition is prepared by sufficiently kneading with a solvent, a diluent or the like, and then using the ink composition, for example, gravure printing, offset printing, letterpress printing, screen printing,
Using printing methods such as transfer printing, flexographic printing, etc., characters, graphics, symbols,
A printed pattern layer according to the present invention can be formed by printing a desired printed pattern composed of a pattern or the like. Thus, in the present invention, the above-mentioned polyurethane-based resin is used as a main component of the vehicle as an ink vehicle, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, UV absorbers, curing agents, cross-linking agents, lubricants, antistatic agents, fillers, arbitrarily add one or more of additives such as other, further, colorants such as dyes and pigments,
The ink composition is prepared by sufficiently kneading with a solvent, a diluent or the like, and then using the ink composition, for example, gravure printing, offset printing, letterpress printing, screen printing,
Using a printing method such as transfer printing, flexographic printing, or the like, a desired printing pattern consisting of characters, figures, symbols, patterns, etc. is printed on the above-mentioned coating thin film, and the printing pattern according to the present invention is obtained. It is desirable to form a layer. In the present invention, as the ink vehicle, by using a polyurethane resin as described above, the reason is not clear, but as described above, the elongation of the thin film constituting the print pattern layer is improved, for example, It is intended to improve the suitability for post-processing such as laminating or bag-making, and to prevent the occurrence of cracks in the inorganic oxide thin film during post-processing.

Next, in the present invention, the heat-sealing resin forming the heat-sealing resin layer constituting the laminated material according to the present invention can be melted by heat and fused to each other. Resin films or sheets can be used, and specifically, for example, 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-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methyl Polyolefin resin such as pentene polymer, polybutene polymer, polyethylene or polypropylene Acid-modified polyolefin resin modified with unsaturated carboxylic acid such as luic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin And other resin films or sheets can be used. Thus, in the present invention, a heat-sealing resin layer can be formed by using the above-mentioned resin film or sheet and laminating them by, for example, a dry lamination method. Things. Alternatively, in the present invention, a heat-sealing resin layer can be formed by a melt extrusion lamination method in which a resin is melt-extruded and laminated. In the present invention, the thickness of the heat-sealing resin layer is preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

Next, in the present invention, in the laminated material according to the present invention, in addition to the above-mentioned materials,
For example, a resin film or sheet having strength and toughness and having heat resistance can be laminated,
Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polyolefin resin,
A film or sheet of a tough resin such as a polycarbonate resin, a polystyrene resin, a polyacetal resin, a fluorine resin, or the like can be used. As the resin film or sheet, any of an unstretched film and a stretched film stretched in a uniaxial or biaxial direction can be used. The thickness of the film is 5μm
To about 100 μm, preferably 10 μm to 50
μm is desirable. In the present invention, for example, characters, graphics, symbols, patterns,
A desired printed pattern such as a pattern may be subjected to front printing or back printing by a normal printing method.

Next, in the present invention, for example, various paper substrates constituting a paper layer can be used and laminated, and specifically, in the present invention, It has moldability, bending resistance, rigidity, etc.,
For example, a strong size bleached or unbleached paper substrate, or a paper substrate such as pure white roll paper, kraft paper, paperboard, or processed paper;
Others can be used. In the above, the paper base material constituting the paper layer has a basis weight of about 80 to 600 g / m.
^Second place, preferably about 100-450 g / m basis weight
It is desirable to use the ^second place. Of course, in the present invention, a paper substrate constituting the paper layer and various resin films or sheets as the above-mentioned substrate film can be used in combination.

Further, in the present invention, as a material constituting the laminated material according to the present invention, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density Polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or, oxygen, polyvinylidene chloride having a barrier property against water vapor,
Film or sheet of resin such as polyvinyl alcohol or saponified ethylene-vinyl acetate copolymer, light-shielding obtained by adding a colorant such as a pigment to the resin and other desired additives and kneading to form a film. Various colored resin films or sheets having properties can be laminated. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually 5 μm to 300 μm.
And more preferably about 10 μm to 150 μm.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the packaging material constituting the packaging container. And various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing property, quality maintenance, workability, hygiene, etc. are required. A material that satisfies the above conditions can be arbitrarily selected and used.Specifically, for example, 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 copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Chillpentene 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, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluororesin,
Any known resin film or sheet such as a diene resin, a polyacetal resin, a polyurethane resin, nitrocellulose, or the like can be used. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extruded film, an inflation film, or a coating film. Further, in the present invention, any one of the layers constituting the laminated material according to the present invention may be formed by, for example, offset printing, gravure printing, silk screen printing, etc. It goes without saying that a print pattern layer can also be formed.

Next, a method of manufacturing a laminated material using the above-described materials in the present invention will be described.
For example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die extrusion molding, co-extrusion lamination, inflation, It can be performed by an extrusion inflation method or the like. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, a pretreatment such as a corona treatment or an ozone treatment can be performed on the film, and for example, an isocyanate-based (urethane) Series), polyethyleneimine series, polybutadiene series, organic titanium series etc.
Coating agents or adhesives for laminating polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., 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-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer,
A polyolefin resin such as ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, or polyethylene or polypropylene can be used with acrylic, methacrylic, maleic, maleic anhydride, fumaric acid, itaconic acid, etc. Known pretreatments such as a melt-extruded resin layer of an acid-modified polyolefin resin modified with a saturated carboxylic acid, an anchor coating agent, an adhesive, and the like can be used.

In the present invention, the laminating adhesive layer constituting the laminate according to the present invention will be described. The laminating adhesive layer includes the above-mentioned polyfunctional isocyanate and hydroxyl group. One- or two-component curable laminating adhesive layers mainly composed of a polyurethane resin obtained by reaction with a compound contained therein can be used. Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or hexamethylene diisocyanate, xylylene diisocyanate 1 obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a naat with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol or the like. An adhesive composition containing a liquid or two-component curable polyurethane resin as a main component of the vehicle is used, for example, a roll coat, a gravure coat.
The present invention is applied to the entire surface including the above-mentioned printed pattern layer by coating, knife coating, dip coating, spray coating and other coating methods, and then drying the solvent, diluent, etc. The laminating adhesive layer constituting the laminate can be formed. In the above, the thickness of the adhesive layer is desirably about 0.1 to 6 g / m ² (dry state). Thus, in the present invention, by using the above-mentioned polyurethane resin, the elongation of the thin film constituting the adhesive layer is improved in the same manner as described above. The purpose is to improve the suitability for post-processing such as bag processing and prevent the occurrence of cracks and the like in the inorganic oxide thin film during post-processing.

In the present invention, the laminating adhesive layer constituting the laminated material according to the present invention may be a dumbbell No. 4 according to JIS K6301.
300 mm / min. In an environment of 50 ° C. and 50% RH. It is desirable that the material has a tensile elongation of 300% to 550% when measured under the following speed conditions. In the present invention, the tensile elongation of the adhesive layer is determined by the aforementioned core.
A thin film, a printing pattern layer, etc., and a deposition film of an inorganic oxide constituting a laminated material, a primer agent layer, a printing pattern layer,
It is intended to improve the tight adhesion with an adhesive layer, a heat-sealing resin layer, and the like, thereby preventing the occurrence of cracks and the like in a deposited film of an inorganic oxide. In the above, if the tensile elongation is less than 300%, it lacks flexibility,
In post-processing such as bag making or box making, cracks and the like are generated in the deposited film of the inorganic oxide, which is not preferable. This is not preferable because of poor intactness, for example, inferior in opening property of the packaging container. In the present invention, if necessary, a cellulose derivative such as nitrocellulose, and other binders may be optionally added to the polyurethane resin composition as described above. Can be done.

In the production of the laminated material according to the present invention, if necessary, for example, at the time of laminating, for example, an organic titanium-based anchor coating agent such as alkyl titanate, an isocyanate-based anchor coating may be used. Agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, and the like can be used. Thus, in the present invention, for example, roll coat, gravure coat,
Coating by knife coating, dip coating, spray coating, or other coating methods, drying the solvent, diluent, etc., and then anchor coating with the anchor coating agent according to the present invention. An agent layer can be formed. In the above, the coating amount of the anchor coating agent is 0.1 to 5 g.
/ M ² (dry state).

Next, in the present invention, a method of making a bag or a box using the above-mentioned laminated material will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, Using a laminated material manufactured by such a method, the heat-sealing resin layer of the inner layer is made to face the surface, and it is folded or the two sheets are overlapped, and furthermore, the peripheral edge portion is formed. A bag can be formed by providing a seal portion by heat sealing. Thus, as a bag making method, the above-described laminated material is folded with its inner layer facing the surface, or the two are laminated,
Further, the peripheral end portion of the outer periphery is formed, for example, by a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, and a gasket-attached seal type ( According to the present invention, a heat seal is formed according to a heat seal form such as a (pyrro-seale type), a pleated seal type, a flat bottom seal type, a square bottom seal type, and the like. Various forms of packaging containers can be manufactured. Others, for example, self-supporting packaging bags (standing pouches)
Can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-mentioned laminated material. In the above, as a method of heat sealing, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal,
Can be performed by a known method such as In the present invention, a spout such as a one-piece type, a two-piece type, etc., or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container containing a paper substrate as a packaging container, for example, a laminated material in which a paper substrate is laminated is produced as a laminated material, and a desired paper container is produced therefrom. A blank plate is manufactured, and thereafter, a body, a bottom, a head and the like are manufactured using the blank plate to manufacture, for example, a liquid paper container of a brick type, a flat type or a gable-top type. be able to. Moreover, the shape can be manufactured by any of a rectangular container, a circular paper can and the like.

In the present invention, the packaging containers produced as described above include various foods and beverages such as liquid beverages, confectionery, powdery, liquid or solid seasonings, and other adhesives, adhesives and pressure-sensitive adhesives. It is used for filling and packaging of various articles such as chemicals, detergents, cosmetics such as others, pharmaceuticals, miscellaneous goods such as chemical warmers, and others. The laminated material according to the present invention can be used as a lid material, for example, by being attached to a flange portion of a plastic molded container.

[0043]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). A plasma chemical vapor deposition apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. Further, one surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as the base film is previously subjected to a corona discharge treatment, and has a static and dynamic friction coefficient of 0.60 μm, respectively. , 0.56μ. The above static and kinetic friction coefficients are values obtained by measuring the static friction coefficient and the kinetic friction coefficient at 50 mm / min with a slip tester (Model TR-2) manufactured by Toyo Seiki Seisakusho Co., Ltd. (Examples and Comparative Examples below). The same applies to.). First,
The above-mentioned biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Under the following plasma chemical vapor deposition conditions, a silicon oxide deposited film having a thickness of 150 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Winding chamber-internal vacuum; 6.0 × 10 ^-6 mb
ar Process chamber vacuum degree: 2 to 6.0 × 10 ^-3 mb
ar Cooling / electrode drum supply power; 10 kW line speed; 100 m / min (2). Next, after a silicon oxide vapor deposition film is formed on the surface of the corona treatment layer of the biaxially stretched polyethylene terephthalate film, the silicon oxide vapor deposition film formed above is formed in-line by using a discharge plasma generator. Was subjected to a plasma treatment under the following conditions to form a plasma-treated surface. (Plasma treatment conditions) Glow-discharge gas: oxygen gas [1.0 (unit: slm)] Power supply: DC Discharge power: 60 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treated surface : Silicon oxide deposited film surface (3). On the other hand, as a silane coupling agent, N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, 0.3% by weight of the silane coupling agent,
1.0% by weight of silica powder (particle diameter 2 μm), 15.6% by weight of polyurethane resin, 3.5% by weight of nitrocellulose, a mixture of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2 A polyurethane-based resin composition comprising 79.6% by weight of a solvent was prepared. Next, on the plasma-treated surface after forming the plasma-treated surface in-line, the polyurethane resin composition prepared as described above is used, and this is coated using a gravure roll coating method. Then, the resultant is dried at 120 ° C. for 20 seconds to form a primer layer (thickness: 0.5 g / m ² , dry state) made of the polyurethane resin composition. Manufactured. (4). Next, a desired printing pattern layer of four colors is formed on the surface of the primer agent layer of the barrier film prepared above using a gravure printing method using an ink composition containing a polyurethane resin as a vehicle. After that, the entire surface including the printed pattern layer is coated with polyester polyol and isocyanate.
A laminating adhesive having a thickness of 1 μm is coated by a gravure roll coating method using a laminating adhesive composed of a 7% ethyl acetate solution of a two-component curable polyurethane resin composed of Forming an adhesive layer (dry state) for
Further, a low-density polyethylene film having a thickness of 60 μm was dry-laminated on the surface of the laminating adhesive layer formed as described above to produce a laminated material according to the present invention. Using the laminated material manufactured as described above, a three-way seal-type plastic bag was manufactured by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Embodiment 2 (1). A plasma-enhanced chemical vapor deposition apparatus was used, and a 15 μm thick biaxially stretched nylon 6 was used as a base film.
Film was used. Further, one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm as the above-mentioned base film is subjected to corona discharge treatment in advance, and the static and dynamic friction coefficients are 0.5 μ and 0, respectively. .45μ. First, a biaxially stretched nylon 6 film having a thickness of 15 μm was mounted on a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and then, on the corona-treated surface of the biaxially stretched nylon 6 film under the following vapor deposition conditions. Then, a silicon oxide deposited film having a thickness of 150 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Winding chamber-internal vacuum; 6.0 × 10 ^-6 mb
ar Process chamber vacuum degree: 2 to 6.0 × 10 ^-3 mb
ar Line speed; 100 m / min Cooling / electrode drum supply power; 10 kW (2). Next, after forming a deposited silicon oxide film on the surface of the corona-treated layer of the biaxially stretched nylon 6 film above, using a discharge plasma generator in-line on the surface of the deposited silicon oxide film, Plasma treatment under the conditions of
A plasma treated surface was formed. (Plasma treatment conditions) Glow-discharge gas: oxygen gas [1.0 (unit: slm)] Power supply: DC Discharge power: 60 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treated surface : Silicon oxide deposited film surface (3). On the other hand, γ-glycidoxypropyltrimethoxysilane was used as a silane coupling agent, and 0.3% by weight of the silane coupling agent, 1.0% by weight of silica powder, 15.6% by weight of polyurethane resin, A polyurethane resin composition comprising 3.5% by weight of a solvent and 79.6% by weight of a mixed solvent of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2 was prepared. Using the polyurethane-based resin composition prepared above, this was coated on the plasma-treated surface formed above using a gravure roll coating method, and then at 120 ° C. for 20 seconds. After drying, a primer agent layer (0.2 g / m ² dry state) of the polyurethane-based resin composition was formed to produce a barrier film according to the present invention. (4). Next, on the surface of the primer agent layer of the barrier film produced above, a desired printing pattern composed of four colors was formed by a gravure printing method using an ink composition using a polyurethane resin as a vehicle. Thereafter, a laminating adhesive composed of a 7% ethyl acetate solution of a two-part curable polyurethane resin composed of polyetherpolyol and isocyanate is used on the entire surface including the printed pattern layer. Coating by a gravure roll coating method to give a film thickness of 1
forming an adhesive layer for lamination (dry state) with a thickness of 80 μm, and then dry-laminating a low-density polyethylene film having a thickness of 80 μm on the surface of the adhesive layer for the lamination; Was manufactured. Using the laminated material manufactured as described above, a three-way seal-type plastic bag was manufactured by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Embodiment 3 (1). A plasma enhanced chemical vapor deposition apparatus was used, and a biaxially stretched polypropylene film having a thickness of 20 μm was used as a base film. Further, one surface of a biaxially stretched polypropylene film having a thickness of 20 μm as the above-mentioned base film is subjected to corona discharge treatment in advance, and has a static and dynamic friction coefficient of 0.5 μm and 0.5 μm, respectively.
4μ. First, a biaxially-stretched polypropylene film having a thickness of 20 μm was mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus, and then, on the corona-treated surface of the biaxially-stretched polypropylene film under the following evaporation conditions,
A silicon oxide deposited film having a thickness of 150 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Winding chamber-internal vacuum; 6.0 × 10 ^-6 mb
ar Process chamber vacuum degree: 2 to 6.0 × 10 ^-3 mb
ar Line speed; 100 m / min Cooling / electrode drum supply power; 10 kW (2). Next, after forming a silicon oxide vapor deposition film on the surface of the corona treatment layer of the biaxially stretched polypropylene film, the following surface was formed on the silicon oxide vapor deposition film using an in-line discharge plasma generator. Plasma treatment was performed under the conditions to form a plasma treatment surface. (Plasma treatment conditions) Glow-discharge gas: oxygen gas [1.0 (unit: slm)] Power supply: DC Discharge power: 60 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treated surface : Silicon oxide deposited film surface (3). On the other hand, as a silane coupling agent, N-β
(Aminoethyl) -γ-aminopropyltrimethoxysilane, 0.3% by weight of the silane coupling agent,
1.0% by weight of silica powder (particle diameter 2 μm), 15.6% by weight of polyurethane resin, 3.5% by weight of nitrocellulose, a mixture of toluene, methyl ethyl ketone and isopropyl alcohol in a ratio of 4: 4: 2 A polyurethane-based resin composition comprising 79.6% by weight of a solvent was prepared. Next, on the plasma-treated surface after forming the plasma-treated surface in-line, the polyurethane resin composition prepared as described above is used, and this is coated using a gravure roll coating method. Then, the resultant is dried at 120 ° C. for 20 seconds to form a primer layer (thickness: 0.5 g / m ² , dry state) made of the polyurethane resin composition. Manufactured. (4). Next, a desired printing pattern layer of four colors is formed on the surface of the primer agent layer of the barrier film prepared above using a gravure printing method using an ink composition containing a polyurethane resin as a vehicle. After that, the entire surface including the printed pattern layer is coated with polyester polyol and isocyanate.
An anchor coating agent consisting of a 7% ethyl acetate solution of a two-part curable polyurethane resin consisting of a coating solution and a gravure roll coating method is used to coat the film with a film thickness of 1%.
An anchor coating agent layer (dry state) having a thickness of 60 μm was formed on the surface of the anchor coating agent layer formed above using a low-density polyethylene while melting and extruding the same. The low density polyethylene resin layer was extruded and laminated to produce a laminated material according to the present invention. Using the laminated material manufactured as described above, a three-way seal-type plastic bag was manufactured by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled and packaged product. However, no deterioration of the barrier properties was observed, and extremely good results were obtained.

Comparative Example 1 (1). A plasma chemical vapor deposition apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. Further, one surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as the base film is previously subjected to a corona discharge treatment, and has a static and dynamic friction coefficient of 0.60 μm, respectively. , 0.56μ. First,
The above-mentioned biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. A barrier film was manufactured by forming a silicon oxide deposited film having a thickness of 150 ° under the following plasma chemical vapor deposition conditions. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Winding chamber-internal vacuum; 6.0 × 10 ^-6 mb
ar Process chamber vacuum degree: 2 to 6.0 × 10 ^-3 mb
ar Cooling / electrode drum supply power; 10 kW line speed; 100 m / min (2). Next, an ink composition using a polyurethane-based resin as a vehicle was used on the surface of the silicon oxide vapor-deposited film of the barrier film produced above by a gravure printing method.
After forming a desired print pattern layer composed of a color, the entire surface including the print pattern layer is laminated with a 7% ethyl acetate solution of a two-part curable polyurethane resin composed of polyester polyol and isocyanate. A laminating adhesive layer (dry state) having a film thickness of 1 μm is formed by coating with a gravure roll coating method using an adhesive for laminating. On the adhesive layer
A low-density polyethylene film having a thickness of 60 μm was dry-laminated to produce a laminated material. Using the laminated material manufactured as described above, a three-way seal-type plastic bag was manufactured by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled packaging product.

Comparative Example 2 (1). A plasma chemical vapor deposition apparatus was used, and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film. Further, one surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as the base film is previously subjected to a corona discharge treatment, and has a static and dynamic friction coefficient of 0.60 μm, respectively. , 0.56μ. First,
The above-mentioned biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is mounted on a delivery roll of a plasma-enhanced chemical vapor deposition apparatus. Under the following plasma chemical vapor deposition conditions, a silicon oxide deposited film having a thickness of 150 ° was formed. (Evaporation conditions) Evaporation surface; Corona treated surface Introduced gas amount: hexamethyldisiloxane: oxygen gas: helium = 1.0: 3.0: 3.0 (unit: slm) Winding chamber-internal vacuum; 6.0 × 10 ^-6 mb
ar Process chamber vacuum degree: 2 to 6.0 × 10 ^-3 mb
ar Cooling / electrode drum supply power; 10 kW line speed; 100 m / min (2). Next, after a silicon oxide vapor deposition film is formed on the surface of the corona treatment layer of the biaxially stretched polyethylene terephthalate film, the silicon oxide vapor deposition film formed above is formed in-line by using a discharge plasma generator. Was subjected to a plasma treatment under the following conditions to form a plasma-treated surface to produce a barrier film. (Plasma treatment conditions) Glow-discharge gas: oxygen gas [1.0 (unit: slm)] Power supply: DC Discharge power: 60 W · min / m ² Glow-discharge pressure: 2.0 × 10 ⁻² mbar Plasma treated surface : Silicon oxide deposited film surface (3). Next, on the plasma-treated surface of the barrier film produced above, using an ink composition containing a polyurethane resin as a vehicle, and forming a desired print pattern layer of four colors by a gravure printing method, On the entire surface including the printed pattern layer, a laminating adhesive composed of a 7% ethyl acetate solution of a two-component curable polyurethane resin composed of polyester polyol and isocyanate is used. 1 μm thick by coating
To form a laminating adhesive layer (dry state),
A thickness of 60 is applied to the surface of the laminating adhesive layer formed above.
A laminated material was manufactured by dry laminating a low-density polyethylene film of μm. Using the laminated material manufactured as described above, a three-way seal-type plastic bag was manufactured by a bag making machine. Next, the plastic bag produced above was filled with ham and sausage, and then the opening was heat-sealed to produce a filled packaging product.

Experimental Examples Using the barrier films and the laminates produced in Examples 1 to 3 and Comparative Examples 1 and 2, tests were performed on the following evaluation items, and the data were obtained. Was measured. (1). Measurement of Oxygen Permeability Using a barrier film and a laminated material manufactured as described above, at a temperature of 23 ° C. and a humidity of 90% RH, a measuring device [model name, Oxtran (Mocon) manufactured by MOCON, USA) OXTRAN 2/20)]. (2). Measurement of Water Vapor Permeability Using a barrier film and a laminated material manufactured as described above, at a temperature of 37.8 ° C. and a humidity of 100% RH, a measuring machine manufactured by MOCON, USA [model name, Par
Matran (PERMTRAN 2/20)]. (3). Measurement of Laminate Strength Laminate strength was measured at a T-peel strength at a tensile speed of 50 mm / min with a tensile tester using a sample obtained by cutting each of the laminated materials produced as described above into strips having a width of 15 mm. Was done. The above measurement results are shown in Table 1 below.

[0049] In Table 1 above, the unit of oxygen permeability is (cc / m
² day 23 ° C. 90% RH), and the unit of water vapor permeability is (g / m ² day 40 ° C. 100% RH).
H), and the unit of the laminate intensity is (gf /
15 mm width).

As apparent from Table 1 above, Example 1
Those of Nos. 1 to 3 were superior to those of Comparative Examples 1 and 2 in oxygen barrier properties, water vapor barrier properties, laminate strength and the like.

[0051]

As is apparent from the above description, the present invention provides a surface pretreatment layer before providing an inorganic oxide vapor-deposited film on one surface of a base film, On the surface of the surface pretreatment layer, a plasma-enhanced chemical vapor deposition method is used to provide a vapor-deposited film of an inorganic oxide such as silicon oxide, and further, on the surface of the vapor-deposited film of the inorganic oxide, a plasma-treated surface is provided in-line. Further, a primer film is provided on the plasma-treated surface to produce a barrier film, and a dense inorganic oxide vapor-deposited film is formed on one surface of the base film via a surface pretreatment layer. Since the base film and the inorganic oxide vapor-deposited film have excellent close-adhesion, and a surface of the inorganic oxide vapor-deposited film is provided with a primer agent layer via a plasma-treated surface. Excellent adhesion between the inorganic oxide deposited film and the primer agent layer Moreover, it is excellent in bending resistance, etc., and there is no problem that printing, laminating, bag making, and other post-processes such as printing defects, laminating defects, other problems occur, and the like. The occurrence of cracks and the like in the deposited film of the inorganic oxide is not recognized, and has an extremely high barrier property against oxygen gas or water vapor, and
It is excellent in transparency, and for example, a barrier film useful for filling and packaging various articles such as food and drink, pharmaceuticals, cosmetics, chemicals, electronic parts, and others, and a laminate using the same can be produced. That is.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a barrier film according to the present invention.

FIG. 2 is a schematic cross-sectional view showing a layer configuration of an example of a barrier film according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a layer configuration of an example of a laminate according to the present invention manufactured using the barrier film according to the present invention shown in FIG.

FIG. 4 is a schematic configuration diagram illustrating a configuration of a plasma enhanced chemical vapor deposition apparatus.

[Explanation of symbols]

A Barrier Film A ₁ Barrier Film B Laminate 1 Base Film 2 Inorganic Oxide Vapor Deposition Film 3 Plasma Treatment Surface 4 Primer Agent Layer 5 Surface Treatment Layer 6 Heat Seal Resin Layer

Continued on the front page F term (reference) 4F100 AA17B AA20B AK01A AK04D AK42 AK51C AK51G AK63 AT00A BA03 BA04 BA07 BA10A CC01C CC01G EJ55A EJ61B EJ64A EJ65C EJ65G EJ67C EJ67G GB15 JD03 J04G04 J04G04

Claims (9)

[Claims] 1. An inorganic oxide vapor-deposited film formed by chemical vapor deposition on one surface of a substrate film, and a plasma-treated surface is further provided on the inorganic oxide vapor-deposited surface. A barrier film comprising a primer agent layer provided on the plasma-treated surface. 2. The barrier property according to claim 1, wherein the base film is provided with a surface pretreatment layer in advance before forming an inorganic oxide vapor-deposited film on one surface thereof. the film. 3. The barrier according to claim 1, wherein the base film is provided with a corona treatment layer in advance before forming an inorganic oxide vapor-deposited film on one surface thereof. Film. 4. A surface pretreatment layer having a static and kinetic friction coefficient of 0.4 μm to 0.7 μm before a base film is provided with an inorganic oxide vapor-deposited film on one surface thereof. The barrier film according to any one of claims 1 to 3, characterized in that: 5. The barrier film according to claim 1, wherein the inorganic oxide vapor-deposited film comprises a silicon oxide vapor-deposited film formed by a plasma enhanced chemical vapor deposition method. 6. An inorganic oxide vapor-deposited film having a thickness of 100 to 100.degree.
Claim 1 to Claim 1 characterized in that it comprises 1000 °.
5. The barrier film according to 5. 7. The barrier film according to claim 1, wherein the plasma-treated surface is provided in-line on the surface of the inorganic oxide deposited film. 8. The method according to claim 1, wherein the primer agent layer comprises a coating film of a resin composition containing a polyurethane resin as a main component of the vehicle and further containing a silane coupling agent. 7. The barrier film according to 7. 9. An inorganic oxide vapor-deposited film formed by chemical vapor deposition on one surface of a substrate film, and a plasma-treated surface is further provided on the inorganic oxide vapor-deposited surface. A lamination characterized in that at least a heat-sealing resin layer is provided on a primer agent layer of a barrier film having a structure in which a primer agent layer is provided on the plasma-treated surface. Wood.