JP4357912B2 - Barrier film - Google Patents

Description

  The present invention relates to a barrier film, and more specifically, for example, as a barrier material used for packaging materials and the like, it has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc. The present invention relates to a very useful barrier film in which no decrease in the thickness is observed.

  In recent years, as a barrier material used for packaging materials, for example, silicon oxide or oxidation is applied to one surface of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon 6 film. A transparent barrier film provided with a vapor-deposited film of an inorganic oxide such as aluminum has been developed and proposed, and its trend is drawing attention.

For example, on a transparent plastic film substrate, a vapor transmission rate of 1.0 g / min, in which a vapor deposited film mainly composed of silicon oxide and having a thickness of 50 to 200 nm is provided via an ultrathin film of transparent silicon having a thickness of 0.5 to 20 nm. m ² · 24hrs or less, transparent Haibariya wherein the oxygen permeability 0.5 cc / m is ² · 24hrs or less - films are known (e.g., see Patent Document 1.).

A packaging film is also known in which a SiO _x layer (0 ≦ X <2) and a SiO ₂ film are sequentially laminated on at least one surface of a substrate made of a flexible plastic film (see, for example, Patent Document 2). ).

  Further, a polymer of an organic silicon compound containing plastic material and at least silicon, oxygen, and carbon provided thereon, wherein the composition of silicon, oxygen, and carbon is 15% or more of silicon, 20% or more of carbon, and the rest A gas barrier laminated plastic material comprising a first layer formed of a polymer containing oxygen and a second layer of silicon oxide provided on the first layer is also known (for example, Patent Document 3). reference.).

  Furthermore, a plastic material, a first layer which is a silicon compound thin film having a refractive index of 2.0 to 2.3 provided thereon, and a refractive index of 1.4 to 1. A gas barrier plastic material provided with a transparent silicon compound thin film comprising a second silicon oxide layer 6 and a method for producing the same are also known (for example, see Patent Document 4).

Next, in the transparent vapor deposition film in which the SiO _x film (0 <X ≦ 2) is formed on the base film, the SiO _x film is composed of SiC and SiO _y (Y ≦ 2) from the base film interface. A transparent vapor deposition film is also known in which a mixing layer and an SiO _z layer (1.7 <Z ≦ 2) are sequentially laminated (see, for example, Patent Document 5).

  Further, in a transparent gas barrier material having a transparent gas barrier layer made of an inorganic compound on at least one surface of a substrate made of a transparent polymer, the transparent gas barrier layer is a silicon oxide containing 5 to 40 at% carbon and a first layer made of silicon oxide alone. There is also known a transparent gas barrier material characterized in that it has a laminated structure in which a second layer made of each of these is sequentially formed by a PVD method such as vacuum deposition, sputtering, ion plating or the like, or a plasma activated reaction deposition method (for example, , See Patent Document 6).

  Next, a gas barrier packaging material in which a silicon oxide thin film is formed on at least one surface of a base material, and the thin film is formed on a base material in the order of a rough film and a dense film. A gas barrier packaging material having a structure and a method for producing the same are also known (see, for example, Patent Document 7).

Further, in a coated film composed of a base material made of a polymer film and a coating layer made of a metal or a metal oxide formed on at least one surface of the base material by a vapor deposition method, 1. An amorphous and dense ceramic layer having adhesiveness to a material and a coating layer are sequentially laminated, and the ceramic layer has a density of 2.15 (g / cm ³ ) or more. Also known is a coated film characterized by being an amorphous and dense layer of 2 (g / cm ³ ) or less and a silicon oxide layer having an average film thickness of 20 (nm) to 60 (nm). (For example, refer to Patent Document 8).

  Further, the substrate has a barrier layer provided on at least one surface of the substrate, and the barrier layer is made of silicon oxide and one kind of carbon, hydrogen, silicon, and oxygen A barrier film characterized by being a continuous layer containing at least one compound composed of two or more elements and a method for producing the same are also known (see, for example, Patent Document 9).

  Next, a barrier laminate comprising: forming a thin film of a silicon compound on one surface of a resin film by a low temperature plasma CVD method; and laminating a thin film of a metal or a metal compound on the thin film by a physical vapor deposition method, and The manufacturing method is also known (for example, refer patent document 10).

In addition, a transparent barrier film characterized by comprising two or more layers of an inorganic oxide vapor-deposited film formed by plasma chemical vapor deposition on one surface of a base film, and a laminate using the same Is also known (see, for example, Patent Document 11).
Japanese Patent No. 2889627 (Claims etc.) Japanese Patent No. 2926939 (claims, etc.) Japanese Patent No. 2526766 (claims, etc.) JP-A-7-32531 (Claims etc.) JP-A-7-145256 (Claims etc.) Japanese Patent No. 3319164 (Claims etc.) JP-A-7-304127 (Claims etc.) Japanese Patent No. 3255037 (Claims etc.) JP-A-8-142252 (Claims etc.) JP-A-9-12334 (Claims etc.) Japanese Patent Laid-Open No. 11-348171 (Claims etc.)

  However, in the invention according to the above-mentioned Patent Document 1, the deposited film mainly composed of silicon oxide has an extremely thick film thickness of 50 nm to 200 nm, so that the film has extensibility, flexibility, flexibility, etc. In other words, cracks and the like are likely to occur in the production, processing, etc., and the barrier property often decreases.

Next, in the invention according to Patent Document 2, the adhesion between the base material made of the flexible plastic film and the SiO _x layer is improved, but the second layer is the SiO ₂ film. Therefore, since the SiO ₂ film itself is sparse, the SiO ₂ film has almost no gas barrier property. As a result, in the present invention, the gas barrier property must depend on the gas barrier property of the SiO _x layer only. In other words, the gas barrier property is remarkably inferior, and it is extremely difficult to exhibit an extremely excellent gas barrier property.

  In the invention according to Patent Document 3, the film itself constituting the first layer has no gas barrier property. Therefore, the second layer is laminated on the first layer, and the gas barrier property is obtained by the synergistic effect. Even if it is improved, there is a problem that it is still very difficult to obtain a gas barrier property that is sufficiently satisfactory.

  Next, in the invention according to Patent Document 4, as in the invention according to Patent Document 3, since the film itself constituting the first layer does not have gas barrier properties, Even if the second layer is laminated on top and the gas barrier property is improved by the synergistic effect, there is still a problem that it is still very difficult to obtain a gas barrier property that is sufficiently satisfactory.

Furthermore, in the invention according to Patent Document 5, the mixing layer is formed by simply performing a treatment using plasma on the base film, and as a result, the carbon (C ) The component is taken into the mixing layer to form the mixing layer, and thus the adhesion between the base film and the SiO _z layer is improved by laminating through the mixing layer. layer itself, since it does not have sufficient gas barrier properties, by the SiO _z layer are sequentially stacked on a mixing layer, even with improved gas barrier properties with a synergistic effect, it is a gas barrier by SiO _z layer There is a problem that it is very difficult to manufacture a transparent vapor-deposited film having sufficient gas barrier properties.

Next, in the invention according to Patent Document 6, both the first layer and the second layer are SiO ₂ films. Therefore, the SiO ₂ film has almost no gas barrier property because the film itself is sparse. However, in this invention, there is a problem that only the layer made of silicon oxide containing 5 to 40 at% of carbon in the second layer can exhibit gas barrier properties.

  The invention according to Patent Document 7 is characterized by a two-layer structure in which a thin film is formed on a base material in the order of a rough film and a dense film. Similar to the invention, the sparse film has almost no gas barrier property, and in this invention, there is a problem that only the dense film of the second layer can express the gas barrier property, and it is still extremely excellent. It is far from developing gas barrier properties.

Furthermore, in the invention according to Patent Document 8 described above, an amorphous and dense layer having a density of 2.15 (g / cm ³ ) or more and 2.2 (g / cm ³ ) or less is formed. By controlling the density of the film itself as described above to 2.15 (g / cm ³ ) or more and 2.2 (g / cm ³ ) or less by vapor deposition such as vapor deposition or CVD vapor deposition, On the contrary, in order to form a film having such a density, it is necessary to introduce a very expensive control facility to control the density. .

  In addition, the invention according to the above-mentioned Patent Document 9 has an advantage that it has high barrier properties, is excellent in transparency, flexibility, flexibility, impact resistance, etc., and further has suitability for microwave ovens. However, in terms of gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like, it is not a state that is sufficiently satisfactory for practical use, for example, as a packaging material constituting a retort pouch.

  Next, in the invention according to Patent Document 10 described above, although it has a high gas barrier property, a thin film of metal or metal compound is laminated by physical vapor deposition, so that the thin film has extensibility, flexibility, There exists a problem that it is inferior to flexibility and a crack is easy to enter into the thin film.

  Further, in the invention according to the above-mentioned Patent Document 11, the invention according to the above-mentioned Patent Document 9 is improved, and this is formed by stacking two or more layers of vapor-deposited inorganic oxide films by plasma chemical vapor deposition. However, the deposited films of the inorganic oxides constituting the two layers are composed of thin films having substantially the same composition, configuration, etc., and the thin films are simply two layers. Therefore, oxygen gas, water vapor, etc. that have passed through the inorganic oxide vapor deposition film constituting one layer easily pass through the inorganic oxide vapor deposition film constituting the other layer, and prevent this transmission. Therefore, it is difficult to produce a barrier film having a high gas barrier property.

  As described above, in the conventional transparent barrier film using a thin film of an inorganic oxide such as silicon oxide or aluminum oxide as a barrier layer, the barrier material used for the packaging material is oxygen gas, water vapor, or the like. Although it is possible to prevent permeation, it is the actual situation that the barrier film having a higher gas barrier property is not yet satisfactory.

  Therefore, the present invention provides that the silicon oxide layer constituting the barrier layer is excellent in adhesion to the base film and has excellent spreadability, flexibility, flexibility and the like. For example, as a barrier material used for packaging materials, etc., it has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc. An object of the present invention is to provide a very useful barrier film in which a decrease in gas barrier performance is not observed.

  As a result of various studies to solve the above-described problems, the present inventor has used a polyamide resin film as a base film, a base film made of the polyamide resin film, and a polyamide as the base film A barrier layer provided on one surface of the resin film, and the barrier layer uses at least two film forming chambers, and at least each of the chambers contains an organosilicon compound. Two or more film-forming mixed gases prepared by changing the mixing ratio of each gas component of the film-forming mixed gas composition containing one or more kinds of film-forming monomer gas, oxygen gas, and inert gas The composition is composed of two or more layers of silicon oxide layers formed by plasma chemical vapor deposition using the mixed gas composition for film formation, and each of the silicon oxide layers includes: The film contains carbon atoms. In addition, when a barrier film having a different carbon content is manufactured for each silicon oxide layer, a polyamide-based resin film as a base film is obtained by laminating the silicon oxide layer by plasma chemical vapor deposition. In addition to excellent adhesion between the silicon oxide layer and the silicon oxide layer, the silicon oxide layer has excellent spreadability, flexibility, flexibility, etc., and excellent high barrier properties from the first layer. A film can be formed, and two or more silicon oxide layers are continuously stacked using a plasma chemical vapor deposition apparatus comprising at least two film forming chambers, and Since each of the layers can form a film having a high barrier property, a higher gas barrier property than that of a single layer can be obtained, and further, the film is continuously formed to be open to the atmosphere. By crack It is possible to prevent foreign substances, dust, etc., which are the cause of occurrence, from being mixed between the film forming layers, and the deterioration of the barrier property is not recognized. Further, each silicon oxide layer has carbon in the film. Since it is a discontinuous layer containing atoms and having different carbon contents for each silicon oxide layer, it can completely block the transmission of oxygen gas, water vapor, etc. As a barrier material to be used, it has been found that an excellent gas barrier property that prevents permeation of oxygen gas, water vapor, etc. can be produced, and furthermore, a very useful barrier film that does not show a decrease in performance of the gas barrier property can be produced. The present invention has been completed.

  That is, the present invention comprises at least a polyamide resin film and a barrier layer provided on one surface of the polyamide resin film, and the barrier layer further comprises at least two film forming chambers. Each of the mixed gas compositions for film formation containing at least one kind of organosilicon compound, oxygen gas, and inert gas used for each film formation chamber. Two or more plasma chemical vapor deposition methods using two or more film-forming mixed gas compositions prepared by changing the mixing ratio of gas components, and using each of the film-forming mixed gas compositions to form a film A barrier film, wherein each silicon oxide layer contains carbon atoms, and each silicon oxide layer has a different carbon content. It is about.

  The barrier film according to the present invention has excellent adhesion between a polyamide-based resin film as a base film and a silicon oxide layer by laminating a silicon oxide layer by a plasma chemical vapor deposition method. The silicon oxide layer is excellent in spreadability, flexibility, flexibility, and the like.

  In addition, the barrier film according to the present invention can form a film having excellent high barrier properties from the first layer, and can be formed by plasma chemical vapor deposition comprising at least two film forming chambers. Since two or more silicon oxide layers are continuously laminated using a phase growth apparatus, and each layer can form a film having a high barrier property, it is more than that of a single layer. Furthermore, a higher gas barrier property can be obtained.

  Furthermore, the barrier film according to the present invention can prevent foreign matter, dust, and the like causing cracks from being mixed between the film forming layers by continuously forming a film that opens to the atmosphere. And the fall of the barrier property is not recognized.

  Moreover, since the barrier film according to the present invention is a discontinuous layer in which each silicon oxide layer contains carbon atoms in the film and the carbon content differs for each silicon oxide layer, Permeation of oxygen gas, water vapor, etc. can be completely prevented.

  Thus, the barrier film according to the present invention has the above-described effects, and as a barrier material used for, for example, a packaging material, a gas barrier that prevents permeation of oxygen gas, water vapor, and the like. Further, the present invention relates to a very useful barrier film in which the gas barrier property is not deteriorated and the gas barrier property is not deteriorated.

  The barrier film according to the present invention will be described below in more detail with reference to the drawings.

  FIG. 1 and FIG. 2 are schematic configuration diagrams showing the schematic configuration of one example of the production apparatus for the barrier film according to the present invention, and FIG. 3 is the layer configuration of the barrier film according to the present invention. It is a schematic sectional drawing which shows an example.

  First, the production method of the barrier film according to the present invention will be described. The barrier film according to the present invention is produced, for example, by forming a silicon oxide layer using a chemical vapor deposition method or the like. Specifically, for example, a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like is used. It can be produced by forming a silicon oxide layer, and among them, it is particularly desirable to produce it by using a low temperature plasma chemical vapor deposition method.

  In the present invention, specifically, on one surface of a base film made of a polyamide-based resin film, a film-forming monomer gas composed of one or more organic silicon compounds is used as a raw material, and argon is used as a carrier gas. Silicon oxide using a low temperature plasma chemical vapor deposition method using an inert gas such as a gas or helium gas, further using oxygen gas as an oxygen supply gas, and using a low temperature plasma generator or the like A barrier film according to the present invention can be manufactured by forming a silicon oxide layer made of, for example, a film.

  In the above, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator.

  Specifically, the manufacturing method of the barrier film according to the present invention will be described. FIG. 1 shows the present invention using a low-temperature plasma chemical vapor deposition apparatus that forms a silicon oxide layer by plasma chemical vapor deposition. It is a schematic block diagram which shows the outline | summary about the plasma chemical vapor deposition apparatus which manufactures the barrier film concerning invention.

  In the present invention, as shown in FIG. 1, the plasma chemical vapor deposition apparatus 1 includes a polyamide-based resin film supply chamber 2 as a base film, a first film formation chamber 3, and a second film formation chamber 4. , A third film forming chamber 5 and a winding chamber 6 for winding up the barrier film according to the present invention in which a silicon oxide layer is formed and laminated on a polyamide resin film as a base film. Is the basic structure.

  Thus, in the present invention, first, the polyamide resin film 8 wound around the unwinding roll 7 is fed out to the first film forming chamber 3, and further, the polyamide resin film 8 is supported as an auxiliary material. It is conveyed on the circumferential surface of the cooling / electrode drum 10 through the roll 9 at a predetermined speed.

  Next, in the present invention, a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds are supplied from the raw material volatilization supply device 11 and the gas supply device 12 or the like. The film-forming mixed gas composition is introduced into the first film-forming chamber 3 through the raw material supply nozzle 13 while adjusting the film-forming mixed gas composition composed of them, and the cooling / electrode A first silicon oxide layer made of silicon oxide or the like is formed by generating plasma by glow discharge plasma 14 on the polyamide resin film 8 conveyed on the peripheral surface of the drum 10 and irradiating it. Form a film.

  Next, the polyamide resin film 8 obtained by forming the first silicon oxide layer in the first film forming chamber 3 is transferred to the second film forming chamber 4 via the auxiliary rolls 15 and 16. Next, in the same manner as described above, the polyamide-based resin film 8 formed with the first silicon oxide layer is transported onto the cooling / electrode drum 17 peripheral surface at a predetermined speed.

  Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 18, the gas supply device 19, etc. are used to form a film-forming monomer gas, oxygen gas, inert gas comprising at least one organic silicon compound, While supplying the other, adjusting the film-forming mixed gas composition comprising them, introducing the film-forming mixed gas composition into the second film-forming chamber 4 through the raw material supply nozzle 20, and The glow discharge plasma 21 is formed on the first silicon oxide layer of the polyamide-based resin film 8 obtained by forming the first silicon oxide layer conveyed on the circumferential surface of the cooling / electrode drum 17. A plasma is generated by irradiating and irradiating the plasma to form a second silicon oxide layer made of silicon oxide or the like.

  Further, in the present invention, in the same manner as described above, the polyamide-based resin film 8 in which the first layer and the second silicon oxide layer are formed in the second film forming chamber 4 is used as an auxiliary roll. The polyamide resin film 8 in which the first and second silicon oxide layers are formed in the same manner as described above is then fed to the third film forming chamber 5 through 22, 23, etc. Then, it is conveyed on the circumferential surface of the cooling / electrode drum 24.

  Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 25, the gas supply device 26 and the like are used to form a film-forming monomer gas composed of one or more organic silicon compounds, oxygen gas, inert gas, The above-mentioned mixed gas composition for film formation is introduced into the third film forming chamber 5 through the raw material supply nozzle 27 while supplying the other and the like, and adjusting the mixed gas composition for film formation composed of them, and On the second silicon oxide layer of the polyamide-based resin film 8 obtained by forming the first and second silicon oxide layers conveyed on the cooling / electrode drum 24 peripheral surface, Plasma is generated by the glow discharge plasma 28 and irradiated to form a third silicon oxide layer made of silicon oxide or the like.

  Next, in the present invention, the first layer, the second layer, and the third layer of the silicon oxide layer are formed as described above, and the polyamide-based resin film 8 in which these layers are laminated is interposed through the auxiliary roll 29. The barrier film according to the present invention in which the silicon oxide layers of the first layer, the second layer, and the third layer are overlaid on the winding roll 30 and then wound on the winding roll 30. Can be manufactured.

  In the present invention, the cooling / electrode drums 10, 17, and 24 disposed in the first, second, and third film forming chambers 3, 4, and 5 2 and a power source 31 disposed outside the third film forming chambers 3, 4, and 5, and a predetermined power is applied to the cooling and electrode drums 10, 17, and 24. The generation of plasma is promoted by arranging the magnets 32, 33, and 34.

  Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump or the like, and it is needless to say that each film forming chamber can be prepared to be kept in vacuum.

  The above exemplification is an example, and it is needless to say that the present invention is not limited thereby.

  For example, in the above example, the barrier film according to the present invention in which the first layer, the second layer, and the third layer of the silicon oxide layer are overlaid is manufactured. A film chamber can be arbitrarily prepared, and a silicon oxide layer such as two layers or four layers or more can be arbitrarily formed, and can be formed into a layered structure. However, the present invention is not limited to the example of producing the barrier film according to the present invention in which the silicon oxide layers of the first layer, the second layer, and the third layer are overlaid.

  Next, in the present invention, as another example of the plasma chemical vapor deposition apparatus for producing the barrier film according to the present invention, as shown in FIG. 2, the plasma chemical vapor deposition apparatus shown in FIG. 1, a raw material volatilization supply device 11, 18, 25, and a gas supply device 12, 19, 26, etc. are used to form a film-forming monomer gas, oxygen gas, inert gas, etc. Etc., and adjusting the mixed gas composition for film formation comprising them, the raw material supply nozzles 13, 20, 27 and the above into the first, second, third film formation chambers 3, 4, 5. Instead of introducing the mixed gas composition for film formation, by providing two raw material supply nozzles in one film formation chamber, that is, two raw material supply nozzles 13 in the first film formation chamber 3, 13a is provided as a raw material volatilization supply device. 1, 11, and gas supply devices 12, 12 and the like supply vapor deposition monomer gas, oxygen gas, inert gas, etc., which are composed of one or more organic silicon compounds, and a film-forming mixture comprising them. While adjusting the gas composition, the mixed gas composition for film formation is introduced into the first film forming chamber 3 from the two raw material supply nozzles 13 and 13a, and the cooling / electrode drum is The first silicon oxide layer made of silicon oxide or the like is manufactured by generating plasma by glow discharge plasma 14 on the polyamide resin film 8 conveyed on the 14 circumferential surface and irradiating it. In the same manner as described above, the second film forming chamber 4 is provided with two raw material supply nozzles 20 and 20a. From the raw material volatilization supply devices 18 and 18 and the gas supply devices 19 and 19 and the like, From one or more organic silicon compounds A film-forming monomer gas, oxygen gas, inert gas, and the like are supplied, and a film-forming mixed gas composition composed of these is supplied to the second through the two raw material supply nozzles 20 and 20a. The above-described mixed gas composition for film formation is introduced into the film forming chamber 4 and the first silicon oxide layer conveyed on the peripheral surface of the cooling / electrode drum 17 is formed into a polyamide. Plasma is generated by glow discharge plasma 21 on the first silicon oxide layer of the system resin film 8 and irradiated to produce a second silicon oxide layer made of silicon oxide or the like. Further, in the same manner as described above, two raw material supply nozzles 27 and 27a are provided in the third film forming chamber 5, and from the raw material volatilization supply devices 25 and 25 and the gas supply devices 26 and 26, etc. Monomer gas for film formation comprising at least one organic silicon compound, Oxygen gas, inert gas, etc. are supplied, and the mixed gas composition for film formation composed of them is adjusted, and the third film forming chamber 5 is passed through the two raw material supply nozzles 27 and 27a. The polyamide-based resin film in which the mixed gas composition for film formation is introduced, and the first and second silicon oxide layers formed on the cooling / electrode drum 24 are formed into a film. Plasma is generated by glow discharge plasma 28 on the second silicon oxide layer 8 and irradiated to form a third silicon oxide layer made of silicon oxide or the like, Next, in the present invention, the first layer, the second layer, and the third layer of the silicon oxide layer are formed as described above, and the polyamide-based resin film 8 in which these layers are laminated is interposed through the auxiliary roll 29. To the take-up chamber 6 and then to the take-up roll 30 Taken, the first layer, second layer, and is one that can be silicon oxide of the third layer layer to produce a barrier film according to the present invention was overlaid.

In the above, each film forming chamber is depressurized by a vacuum pump or the like, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to prepare it.

  On the other hand, since a predetermined voltage is applied to each cooling / electrode drum from a power source, glow discharge plasma is generated in the vicinity of the opening of the material supply nozzle in each film forming chamber and the cooling / electrode drum, The glow discharge plasma is derived from one or more gas components in the film-forming gas mixture composition. In this state, the polyamide-based resin film is conveyed at a constant speed, and the glow discharge plasma is used. A silicon oxide layer made of silicon oxide or the like can be formed on the polyamide resin film on the cooling / electrode drum peripheral surface.

At this time, the degree of vacuum in each film forming chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable to adjust the conveyance speed of the polyamide resin film to about 10 to 300 m / min, preferably about 50 to 150 m / min.

  In the present invention, the degree of vacuum in each film forming chamber may be the same or different in each chamber.

  Further, in the raw material volatilization supply device, a film forming monomer gas composed of one or more organic silicon compounds as raw materials is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, The film-forming mixed gas composition is introduced into each film-forming chamber through a raw material supply nozzle while adjusting the film-forming mixed gas composition.

  In this case, as the gas mixing ratio of each gas component of the mixed gas composition for film formation, the content of the monomer gas for film formation composed of one kind of organic silicon compound is about 1 to 40%, and the content of oxygen gas It is preferable that the amount is adjusted in the range of about 0 to 70% and the content of the inert gas is in the range of about 1 to 60%.

  Thus, in the present invention, for each film forming chamber, a film forming mixed gas composition prepared by changing the gas mixing ratio of each gas component of the film forming mixed gas composition introduced into each film forming chamber. A barrier film according to the present invention is manufactured by forming a film for each film forming chamber and overlaying a silicon oxide layer made of silicon oxide or the like.

  That is, in the present invention, the mixing ratio of each gas component of a film-forming mixed gas composition containing at least one monomer gas for forming a film, oxygen gas, and inert gas, which is composed of at least one organic silicon compound. The two or more film-forming mixed gas compositions are prepared, and the film-forming mixed gas composition is arbitrarily changed for each film-forming chamber, and each of these film-forming mixed gas compositions is used. It is possible to form a silicon oxide layer by plasma chemical vapor deposition using two or more layers.

  By the way, in this invention, as mixing ratio of each gas component of said film-forming mixed gas composition, as a 1st film-forming mixed gas composition, monomer gas for film forming: oxygen gas: A mixed gas composition for film formation having a gas composition ratio of inert gas = 1: 0 to 5: 1 (unit: slm, abbreviation for stand-driter-minit), and another second film formation As a mixed gas composition for film formation, a gas composition ratio of film forming monomer gas: oxygen gas: inert gas = 1: 6 to 15: 1 (unit: slm, abbreviation of stand-driter-minit). A film-forming mixed gas composition or the like can be used.

  Thus, in the present invention, the mixed gas composition for film formation as described above is arbitrarily combined, and the mixed gas composition for film formation is placed in the first, second, or third film forming chamber. The film can be formed using a mixed gas composition for film formation in which the mixing ratio of each gas component is changed.

In addition, when forming into a film using the mixed gas composition for film forming which changed the mixing ratio of each gas component of said mixed gas composition for film forming, the 1st mixed gas composition for film forming is used. Then, the carbon amount in the silicon oxide layer formed into a film increases, and there is a tendency that the C—C bond and the Si—CH ₃ bond increase, thereby being highly flexible and high with respect to water vapor. A water-repellent silicon oxide layer having a barrier property can be formed.

In the present invention, when the second mixed gas composition for film formation is used, an appropriate amount of carbon can be contained in the formed silicon oxide layer, and Si—CH ₃ bonds are also appropriate. Thus, a silicon oxide layer having high flexibility and high barrier property against oxygen can be formed.

  Thus, in the present invention, when the film forming mixed gas composition as described above is used to form a film, the order of using the film forming mixed gas composition is, for example, the first manufacturing process. In order of the mixed gas composition for a film and the second mixed gas composition for a film forming, or the first mixed gas composition for forming a film, the second mixed gas composition for forming a film, and the first film forming It is preferable that the mixed gas composition for film formation is introduced into each film forming chamber in order of the mixed gas composition to form a film.

  In the above, by using the first film-forming mixed gas composition in two chambers, it is possible to form a silicon oxide layer having high flexibility and high barrier property against water vapor. It is what you have.

  Furthermore, in the present invention, when the film is formed by the method shown in FIG. 2 described above, for example, the first mixed gas composition for film formation, the second mixed gas composition for film formation, The mixed gas composition for film formation, the mixed gas composition for second film formation, the mixed gas composition for first film formation, and the mixed gas composition for second film formation in this order. It is preferable to introduce a film into each film forming chamber to form a film.

  Thus, in the present invention, by forming the film in the order as described above, the carbon content in the silicon oxide layer becomes a discontinuous layer that is different for each silicon oxide layer, and is flexible. It is possible to make a silicon oxide layer made of a water-repellent film having high properties and a high barrier property against water vapor.

Further, in the plasma chemical vapor deposition apparatus described above, the silicon oxide layer made of silicon oxide or the like is formed into a plasma source gas on the polyamide resin film in each film forming chamber. Since the film is formed into a thin film in the form of SiO _x while being oxidized by the silicon oxide layer, the silicon oxide layer made of silicon oxide or the like to be formed has a multi-layered structure, and each layer is dense. Thus, a thin film having a small gap, spreadability, flexibility, flexibility and the like is obtained. Therefore, the barrier property of silicon oxide made of silicon oxide or the like is formed by a conventional vacuum deposition method or the like. Compared to a silicon oxide layer made of silicon oxide or the like, the layer is much higher, and since it is composed of a multilayered structure, an extremely high and sufficient barrier property can be obtained.

In the present invention, the surface of the polyamide resin film is cleaned by SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the polyamide resin film. This has the advantage that the close adhesion between the silicon oxide layer made of oxide or the like and the polyamide resin film is high.

Furthermore, the degree of vacuum at the time of forming the silicon oxide layer made of silicon oxide or the like as described above is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 The degree of vacuum when forming a silicon oxide layer made of silicon oxide or the like by a conventional vacuum deposition method is adjusted to 1 × 10 ⁻² Torr, and 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr. Since the degree of vacuum is low compared to the position, it is possible to shorten the time for setting the vacuum state of the polyamide-based resin film at the time of replacing the raw material, it is easy to stabilize the degree of vacuum, and the film forming process is stabilized. .

Further, in the present invention, a silicon oxide layer made of silicon oxide or the like formed using a vapor deposition monomer gas made of one or more organic silicon compounds formed in each film forming chamber is an organic material. A vapor-deposited monomer gas composed of at least one silicon compound and oxygen gas reacts chemically, and the reaction product is closely bonded to one surface of the polyamide-based resin film to provide a dense and flexible thin film. it is intended to form a generally formula SiO _X (provided that, X is a number from 0 to 2) is made of a continuous form of a thin film mainly composed of silicon oxide represented by.

Thus, the silicon oxide layer formed in each of the film forming chambers has a general formula SiO _x (where X is 1.3 to 1.9) in terms of transparency, barrier properties, and the like. It is preferable that the thin film is mainly composed of a silicon oxide represented by:

  In the above, the value of X varies depending on the molar ratio between the vapor-deposited monomer gas and oxygen gas composed of one or more organic silicon compounds, the energy of the plasma, etc. Although the transmittance is small, the film itself is yellowish and the transparency is poor.

  In the present invention, the silicon oxide layer made of silicon oxide or the like formed in each film forming chamber is mainly composed of silicon oxide, and further, one kind of carbon, hydrogen, silicon or oxygen. Or a vapor deposition film containing at least one compound composed of two or more elements by chemical bonding or the like.

  For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like.

Specific examples include hydrocarbons having CH ₃ sites, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.

  In addition to the above, it is possible to change the type, amount, and the like of the compound contained in the silicon oxide layer formed in each film forming chamber by changing the conditions of the film forming process.

  Thus, the content of the above-mentioned compound in the silicon oxide layer formed in each film forming chamber is about 0.1 to 50%, preferably about 5 to 20%. Is.

  In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, flexibility, flexibility, etc. of the silicon oxide layer formed in each film forming chamber are not good. It becomes sufficient, and scratches, cracks, etc. are likely to occur due to bending, etc., and it becomes difficult to stably maintain high barrier properties, and if it exceeds 50%, the barrier properties are lowered, which is not preferable. .

Furthermore, in the present invention, in the silicon oxide layer formed in each film forming chamber, the content of the above compound is preferably increased from the surface of each silicon oxide layer in the depth direction. Thus, on the surface of each silicon oxide layer, the impact resistance and the like can be enhanced by the above compound and the like, and on the other hand, at the interface with the polyamide resin film, the content of the above compound is large . This has the advantage that the adhesion between the polyamide-based resin film and the silicon oxide layer, the adhesion between the silicon oxide layer and the silicon oxide layer, or the like becomes strong.

  Thus, in the present invention, for the silicon oxide layer formed in each film forming chamber, for example, an X-ray photoelectron spectrometer (XPS), a secondary ion mass spectrometer (Secondary Ion) The above physical properties are confirmed by performing elemental analysis of each silicon oxide layer using a method of analysis by ion etching or the like in the depth direction using a surface analyzer such as Mass Spectroscopy (SIMS). be able to.

Moreover, in this invention, the silicon oxide layer formed into a film using said 1st mixed gas composition for film forming has 150-200 O atoms with respect to 100 Si atoms, and 50-50 C atoms. consists 100 component proportions, further, there is IR absorption based on Si-O-Si stretching vibration between 1030cm ^-1 ~1060cm ^-1, and, based on the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 IR It is characterized by absorption.

Thus, the above is because the silicon oxide layer contains a carbon component and contains many C—C bonds and Si—CH ₃ bonds. This shows that the peak position of the IR absorption based on is shifted toward decreasing.

  That is, it can be confirmed that the film is highly water-repellent and has a high barrier property against water vapor.

Furthermore, in this invention, the silicon oxide layer formed into a film using said 2nd mixed gas composition for film forming has 150-200 O atoms with respect to 100 Si atoms, and 50 or less C atoms. made from component ratio, further, there is IR absorption based on Si-O-Si stretching vibration between 1045cm ^-1 ~1075cm ^-1, and the IR absorption based on Si-CH3 stretching vibration 1274 ± 4 cm ^-1 It is characterized by being.

Therefore, the above-described phenomenon is caused by a peak of IR absorption based on Si—O—Si stretching vibration because the silicon oxide layer contains few carbon components and contains only Si—CH ₃ bonds. The position indicates that there is no shift.

  That is, it can be confirmed that the film is highly flexible and has a high barrier property against oxygen.

  Next, in the present invention, the total film thickness of the silicon oxide layer formed in each film forming chamber constituting the barrier layer is preferably about 60 to 4000 mm, specifically, The film thickness is preferably about 100 to 1000 mm, and in the above, it is not preferable that the film is thicker than 1000 mm, more preferably 4000 mm, because cracks are easily generated in the film. Is less than 60 mm, it is not preferable because it is difficult to achieve a barrier effect.

  In the present invention, as the film thickness of each silicon oxide layer formed in each film forming chamber constituting the barrier layer, first, as the film thickness of the silicon oxide layer constituting the first layer Is about 20 to 200 mm, preferably 30 to 100 mm, and the thickness of the silicon oxide layer constituting the second layer is about 20 to 200 mm, preferably about 30 to 100 mm. Further, the film thickness of the silicon oxide layer constituting the third layer is preferably about 20 to 200 mm, more preferably about 30 to 100 mm.

  In the above, if it is 20 mm or less, its own barrier properties are not expressed, and if it exceeds 200 mm, cracks and the like are likely to occur in the film. In particular, the base film is wound during film formation. This is not preferable because cracks tend to be easily formed.

  In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.

  In the above, as a means for changing the film thickness of the silicon oxide layer, the volume velocity of the layer is increased, that is, a method for increasing the amount of the monomer gas for forming a film and the amount of oxygen gas. It can be performed by a method of slowing the film forming speed.

  Next, in the present invention, examples of the organosilicon compound constituting the monomer gas for film formation include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, Hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octa Methylcyclotetrasiloxane, etc. can be used.

  In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.

  Moreover, in this invention, argon gas, helium gas etc. can be used as inert gas, for example.

  Next, in the present invention, the base film composed of the polyamide resin film constituting the barrier film according to the present invention will be described. The base film composed of the polyamide resin film has a chemical or physical strength. Use a polyamide-based resin film or sheet that is excellent, can withstand the conditions for forming each silicon oxide layer, etc., and can be maintained well without impairing the film characteristics of the silicon oxide layer, etc. be able to.

  Thus, in the present invention, the polyamide resin film or sheet specifically includes, for example, nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and the like. Various polyamide-based resin films or sheets can be used.

  These polyamide resin films or sheets may be uniaxially or biaxially stretched, and the thickness is about 9 to 200 μm, preferably about 10 to 100 μm.

  In addition, the polyamide resin film or sheet may be subjected to a surface smoothing treatment or the like by coating an anchor coating agent or the like on the surface, if necessary.

  In the present invention, as the above-mentioned various polyamide-based resin films or sheets, for example, one or more of the above-mentioned various polyamide-based resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method are used. A method of forming a film of each of the above-mentioned various polyamide resins by using a film forming method such as an inflation method or the like, or a multilayer coextrusion manufacturing using two or more types of various polyamide resins. Films or sheets of various polyamide resins are manufactured by a method of forming a film, and further, by using two or more kinds of polyamide resins, and by mixing and forming a film before forming a film, If necessary, for example, various polyamide resin films or sheets that are stretched uniaxially or biaxially using a tenter method or a tubular method are used. It can be.

  In the present invention, the film thickness of various polyamide resin films or sheets is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

  In addition, one or more of the above-mentioned various polyamide-based resins are used, and when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, Various plastic compounding agents and additives can be added for the purpose of improving and modifying slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. The amount can be arbitrarily added from a very small amount to several tens of percent 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. Furthermore, a modifying resin or the like can be used.

  In the present invention, the surface of various polyamide-based resin films or sheets may be provided with a desired surface treatment layer in advance, if necessary, in order to improve the close adhesion to the silicon oxide layer. It is something that can be done.

  In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.

  The surface pretreatment is carried out as a method for improving the close adhesion between various polyamide resin films or sheets and the silicon oxide layer. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer is arbitrarily formed in advance on the surface of various resin films or sheets. And it can also be set as a surface treatment layer.

  Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition having a vehicle as a main component of a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

  By the way, the polyamide-based resin film swells due to moisture absorption such as moisture and water vapor, and the dimensional change is about 2 to 10 times as large as that of a commonly used polyester-based resin film as a substrate film for film formation. Therefore, when forming the silicon oxide layer, it becomes extremely difficult for the silicon oxide layer to follow the dimensional change of the polyamide-based resin film. The use of a polyamide-based resin film as a material film must be handled with great care.

  Therefore, in the present invention, as a base film made of a polyamide-based resin film, by providing a water-resistant film on one surface of the polyamide-based resin film, that is, on the surface where the silicon oxide layer is not provided, The polyamide-based resin film can be prevented from swelling and dimensional change due to moisture absorption of moisture, water vapor, etc., and a silicon oxide layer can be satisfactorily formed by chemical vapor deposition.

  Thus, in the present invention, examples of the water-resistant film include a coating film made of a resin composition containing a resin as a main component of a vehicle, or a resin film or sheet laminated. It is possible to use a film or a sheet film.

  Thus, in the present invention, the above-mentioned water-resistant film can be arbitrarily formed off-line or in-line for forming a silicon oxide layer.

  In the above, the resin constituting the main component of the vehicle or the resin constituting the resin film is, for example, a polyolefin resin such as a polyethylene resin, a polypropylene low resin, a chlorinated polypropylene resin, or a poly (meth) acrylic resin. Resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl aceta -Rule resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, Melamine resin, urea resin, polyurethane resin, phenol -Based resin, xylene-based resin, maleic acid resin, nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, and other fibrous resins, chlorinated rubber, cyclized rubber and other rubber-based resins, One type or a mixture of two or more types of resins such as petroleum resins, natural resins such as rosin and casein, and others can be used.

  In general, the polyamide-based resin film has puncture resistance, pinhole resistance, and the like, and has a characteristic that it can be used as a packaging material for filling and packaging contents such as water. , There are drawbacks of high water absorption and poor barrier properties.

  Thus, in the present invention, a polyamide-based resin film is used as the base film, and a plurality of silicon oxide layers are laminated thereon as described above, thereby providing a barrier property, particularly a high barrier property against water vapor. The barrier film can be produced, and is extremely useful as a packaging material as a barrier substrate.

  As apparent from the above description, as shown in FIG. 3, the barrier film according to the present invention produced by forming the film as described above includes a base film 41 made of a polyamide-based resin and the polyamide film. And a barrier layer 42 provided on one surface of a base film 41 made of a resin, and the barrier layer 42 uses at least two film forming chambers, and each film forming chamber. Prepared by changing the mixing ratio of each gas component of the mixed gas composition for film formation containing at least one kind of organosilicon compound, oxygen gas, and inert gas for each film Two or more film-forming mixed gas compositions, and silicon oxide layers 42a, 42b formed by plasma chemical vapor deposition of two or more layers formed using the respective film-forming mixed gas compositions, 42c, and each silicon oxide The layers 42a, 42b, and 42c are mainly composed of silicon oxide, contain at least one compound composed of one or more elements of carbon, hydrogen, silicon, and oxygen, and each silicon oxide The present invention relates to a barrier film A characterized in that each of the physical layers 42a, 42b, and 42c has a structure in which the content of the compound is different.

  Thus, the barrier film according to the present invention is excellent in adhesion between the base film made of polyamide resin film and the silicon oxide layer by laminating the silicon oxide layer by the plasma chemical vapor deposition method. In addition, the silicon oxide layer is excellent in spreadability, flexibility, flexibility, etc., and can form a film excellent in high barrier properties from the first layer, and at least Two or more silicon oxide layers are continuously laminated using a plasma chemical vapor deposition apparatus composed of two or more film forming chambers, and each layer forms a film having a high barrier property. Therefore, it is possible to obtain a higher gas barrier property than that of a single layer. Mixing between film forming layers In addition, each of the silicon oxide layers is mainly composed of silicon oxide, and is one of carbon, hydrogen, silicon, and oxygen. Since it is a discontinuous layer containing at least one kind of compound composed of two or more kinds of elements and having a different content of the above compound for each silicon oxide layer, it can transmit oxygen gas, water vapor, etc. It has various advantages that it can be completely blocked.

  For this reason, the barrier film according to the present invention is excellent in gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., as a barrier material used for packaging materials, etc. It relates to a very useful barrier film in which no decrease is observed.

  That is, in the present invention, the barrier film according to the present invention produced as described above uses this as a barrier material, and other plastic film, paper base material, metal foil or metal plate, cellophane, woven One or two or more kinds of various base materials such as cloth or non-woven fabric, glass plate, etc. are arbitrarily laminated to produce a laminated material having various forms, and thus the laminated material is used as a packaging material. , Optical member, protective sheet for solar cell module, protective film for organic EL display, protective film for film liquid crystal display, packaging material for polymer battery, aluminum packaging material, etc. It can be applied.

  As an example of the method for producing the above laminated material, for example, first, a primer agent layer is formed on the surface of the silicon oxide layer that forms the barrier layer constituting the barrier film according to the present invention. Next, a laminating adhesive layer is formed on the surface of the primer layer, and then a substrate such as a plastic film is provided via the primer layer and the laminating adhesive layer. By laminating the layers using the dry lamination method, laminated materials having various forms can be produced.

  Alternatively, in the present invention, for example, a primer agent layer is first formed on the surface of the silicon oxide layer that forms the barrier layer constituting the barrier film according to the present invention, and then the primer agent layer is formed. An anchor coat agent layer is formed on the surface, and then various resins are melt extruded through the primer agent layer and the anchor coat agent layer to laminate a desired base material. By laminating using the extrusion laminating method, laminated materials having various forms can be produced.

  In the present invention, in the same manner as described above, another base material can be arbitrarily inserted and laminated between the above layers, and the polyamide resin film constituting the barrier film according to the present invention In the same manner as above, other desired base materials can be arbitrarily laminated to produce laminated materials having various forms. In the present invention, the purpose of use, the form of use, and the use thereof In addition, according to others, other base materials can be arbitrarily laminated, and various types of laminated materials can be designed and manufactured.

  Next, in the present invention, a packaging container will be described as an example of use of the above laminated material. In the present invention, for example, two sheets of the above laminated material are prepared as packaging containers. Then, the surfaces of the heat-sealable resin layer located in the innermost layer are made to face each other, and thereafter, the seal part is formed by heat-sealing the three ends of the outer periphery. In addition, a three-sided seal type soft packaging container can be manufactured by providing an opening on the upper side.

  Thus, in the present invention, although not shown, from the opening of the three-sided seal type soft packaging container manufactured above, for example, the contents such as food and drink, etc. are filled, and then the upper Heat seal the opening to form an upper seal, etc., and, if necessary, for example, boil treatment, retort treatment, etc., to produce packaged products of various forms It is something that can be done.

  In the present invention, it goes without saying that the present invention is not limited to the illustrated packaging containers shown above, and depending on the purpose, use, etc., a flexible packaging bag, a liquid paper container, a paper can, It goes without saying that various types of packaging containers such as others can be manufactured.

  Next, in the present invention, the primer agent layer constituting the laminated material will be described. First, as the primer agent layer, a polyurethane resin or a polyester resin is used as a main component of the vehicle, and the polyurethane agent layer The silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and the filler is 0.1 to 20% by weight with respect to 1 to 30% by weight of the resin or polyester resin. , Preferably in a proportion of about 1 to 10% by weight, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. are optionally added, and solvent Then, a diluent or the like is added and mixed well to prepare a polyurethane-based or polyester-based resin composition, and thus the polyurethane-based or polyester-based resin composition is used. For example, the barrier layer constituting the barrier film according to the present invention is formed by a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, or other coating methods. After coating on the surface of the silicon oxide layer to be formed, the coating film is dried to remove the solvent, diluent, etc., and if necessary, an aging treatment or the like is performed. The primer layer according to the invention can be formed.

In the present invention, the film thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state).

  Thus, in the present invention, the primer layer as described above forms a barrier layer constituting the barrier film according to the present invention, a heat-sealable resin layer, The barrier layer according to the present invention at the time of post-processing is improved by improving the post-processability such as laminating processing or bag-making processing. This prevents the generation of cracks in the silicon oxide layer constituting the conductive film.

  In the above, as the polyurethane resin constituting the polyurethane resin composition, for example, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used.

  Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate One obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a salt with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol, or the like. A liquid or two-component curable polyurethane resin can be used.

  Thus, in the present invention, by using the polyurethane-based resin as described above, the close adhesion between the silicon oxide layer and the heat-sealable resin layer is improved and the primer layer is elongated. For example, it improves the suitability of post-processing such as laminating or bag-making, and prevents the silicon oxide layer from cracking during post-processing.

  In the above, the polyester resin constituting the polyester resin composition includes, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton, A thermoplastic polyester resin produced by polycondensation with one or more valent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like.

  In the above, saturated divalent alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2.2- Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic geo- and the like can be used.

  In the present invention, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid Polyethylene terephthalate resin produced by copolycondensation of phthalic acid, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin, terephthalic acid and isophthalic acid And ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like.

  In the present invention, the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to add 1 to 10% by weight.

  Thus, in the present invention, by using the polyester resin as described above, the tight adhesion and the like are improved and the elongation of the primer layer is improved, for example, laminating or The suitability for post-processing such as bag making processing is improved, and the occurrence of cracks and the like in the silicon oxide layer during post-processing is prevented.

  Next, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, γ One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, an aqueous solution of γ-aminopropylsilicone, and the like can be used.

  In the silane coupling agent as described above, a functional group at one end of the molecule, usually chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which is oxidized by silicon. The metal oxide layer or the active group on the film surface of the silicon oxide layer, for example, a functional group such as a hydroxyl group causes a reaction such as a dehydration condensation reaction to cause a silicon oxide layer. A silane coupling agent is modified with a covalent bond or the like on the film surface of the film, and a strong bond is formed on the film surface of the silicon oxide layer of the silanol group itself by adsorption or hydrogen bond.

  On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. -Reacts with substances constituting the adhesive layer, anchor coating layer, other layers, etc. to form a strong bond, and further, the above-mentioned printed pattern layer, laminating adhesive layer, The heat-sealable resin layer is firmly and tightly bonded through the anchor coating agent layer and the like to increase the laminating strength. Thus, in the present invention, the laminating strength is increased. It is possible to form a high-strength laminated structure.

  In the present invention, the inorganic property and organic property of the silane coupling agent are utilized, and the heat-dissipation is effected through the silicon oxide layer and the printed pattern layer, the adhesive layer or the anchor coating agent layer. It improves the tight adhesion with the rusty resin layer, thereby increasing the laminating strength and the like.

  Next, in the present invention, examples of the filler constituting the polyurethane-based or polyester-based resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used.

  Thus, the above-mentioned filler adjusts the viscosity of the polyurethane-based or polyester-based resin composition liquid, improves its coating suitability, and is a silane coupling with a polyurethane-based or polyester-based resin as a binder resin. It binds via an agent to improve the cohesive strength of the coating film.

Next, in the present invention, the laminating adhesive layer constituting the laminated material will be described. Examples of the laminating adhesive layer constituting the laminating adhesive layer include a polyvinyl acetate adhesive and acrylic acid. Homopolymers such as ethyl, butyl, 2-ethylhexyl ester, etc., or polyacrylate adhesives comprising these and copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene Ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimides, and the like, and copolymers of vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid and other monomers -Based adhesive, amino resin-based adhesive made of urea resin or melamine resin, phenolic resin-based adhesive Epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, rubber adhesives such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone adhesives, alkali metal silicates It is possible to use an inorganic adhesive made of low-melting glass or the like, and other adhesives.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film / sheet type, powder type, solid type, etc. Any form may be used, and the adhesion mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, the above adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method or the like, or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, the anchor coat agent layer constituting the laminated material will be described. As the anchor coat agent constituting the anchor coat agent layer, for example, alkyl titanate or the like is used. Various aqueous or oil-based anchor coating agents such as organic titanium, isocyanate, polyethyleneimine, polyptadiene, etc. can be used.
The above-mentioned anchor coating agent can be coated using a coating method such as a roll coat, a gravure roll coat, a kiss coat, and the like. The amount is preferably 0.1 to 5 g / m ² (dry state).

Examples of the melt-extruded resin layer in the melt-extrusion laminating method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, saps. 1 of thermoplastic resins such as phosphorus resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. Species or two or more can be used.
In the melt extrusion lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed through an anchor coating agent layer such as the above-described anchor coating agent.

Next, in the present invention, as a base material such as a plastic film for forming the innermost layer of the laminated material, for example, a heat-seal resin film or sheet that can be melted by heat and fused to each other is used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α-olefin polymerized using a metallocene catalyst Copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer Polymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene Polyolefin resins such as pyrene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meta ) A film or sheet of a resin such as an acrylic resin, a polyvinyl chloride resin, or the like can be used.
Thus, the above film or sheet can be used in the state of a coating film made of a composition containing the resin.
The thickness of the film or film or sheet is preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

Furthermore, in the present invention, as a base material such as a plastic film constituting the above laminated material, for example, as a basic material of the laminated material, excellent properties in mechanical, physical, chemical, etc. In particular, a resin film or sheet having strength, toughness, and heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid Films, sheets, etc. of tough resins such as resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. can be used. .
Thus, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm.
In the present invention, the base film as described above is subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as letters, figures, symbols, patterns, patterns, etc., for example. May be.

Next, in the present invention, as the base material constituting the laminated material, for example, various paper base materials constituting the paper layer can be used. Specifically, in the present invention, Materials include formability, bending resistance, rigidity, etc., for example, strong sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used.
In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² .
Of course, in the present invention, the paper base material constituting the paper layer and various resin films or sheets as the base film mentioned above can be used in combination.

Furthermore, in the present invention, examples of the material constituting the laminated material include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, and ethylene having barrier properties such as water vapor and water. -Resin film or sheet such as propylene copolymer, or polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, nylon MXD6 resin having barrier properties against oxygen, water vapor, etc. Films or sheets of the above-mentioned resins, colorants such as pigments to the resin, and other various colored resin films or sheets having light-shielding properties obtained by kneading into a film by adding desired additives. Can be used.
These materials can be used alone or in combination.
The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In the present invention, usually, when the above laminated material is applied to various applications, it is subjected to severe conditions both physically and chemically. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. Can be used by arbitrarily selecting a material that satisfies the above-mentioned conditions. 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, methyl Pentene 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, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can select and use.
In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

  Thus, in the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film, and for example, isocyanate (urethane) Type), polyethyleneimine type, polybutadiene type, organic titanium type anchor coating agent, or polyurethane type, polyacrylic type, polyester type, epoxy type, polyvinyl acetate type, cellulose type, etc. -Known pretreatments such as adhesives for coating, anchor coating agents, adhesives, and the like can be used.

In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminated material.
Thus, the printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet ray, and the like. One or more additives such as an absorbent, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are arbitrarily added, and a colorant such as a dye / pigment is added, and a solvent is added. The ink composition is prepared by sufficiently kneading with a diluent, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. The printing pattern layer according to the present invention can be formed by printing a desired printing pattern composed of characters, figures, symbols, patterns, etc. on the above-described coating thin film using a printing method such as .

In the present invention, the primer agent layer provided on the surface of the silicon oxide such as silicon oxide or aluminum oxide, in addition to the primer agent layer made of the polyurethane-based or polyester-based resin composition, For example, a polyamide resin, an epoxy resin, a phenol resin, a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aly polypropylene, or a copolymer or modified resin thereof, cellulose The primer agent layer can be formed by using a resin composition containing a glass resin, etc. as a main component of the vehicle.
In the present invention, for example, a primer coating layer is formed by coating using a coating method such as roll coating, gravure rolling coating, kiss coating, etc. Therefore, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, a description will be given of a bag making or box making method for manufacturing a packaging container using the above-described laminated material. For example, when the packaging container is a flexible packaging bag made of a plastic film or the like Using the laminated material manufactured by the method as described above, facing the heat-sealable film of the inner layer facing each other, folding them up or stacking the two sheets, The bag body can be configured by heat sealing the portion to provide a seal portion.
Thus, as a bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of a heat sealing such as a flat bottom sealing type, a square bottom sealing type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, 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 including a paper base material as a packaging container, for example, as a laminated material, a laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared from this After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. .
Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container produced as described above is used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is what is used.
Thus, in the present invention, in particular, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a sachet for filling and packaging rice cake, a soft packaging bag for filling and packaging fresh confectionery, etc. It is useful as a packaging container for filling and packaging foods and beverages such as soft packaging bags for filling and packaging boiled or retort foods.

Hereinafter, the present invention will be described in more detail with reference to examples.
A biaxially stretched nylon 6 film having a thickness of 15 μm was prepared as a base film, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas and inert gas helium supplied from the gas supply device. The raw material gas was used.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is set to HMDSO: O ₂ : He = 1: 0: 1 (unit: slm, standard driter-minit), and the second As a raw material gas used in the film forming chamber, the mixing ratio of the raw material gases was HMDSO: O ₂ : He = 1: 10: 1 (unit: slm).
The third film forming chamber was not used.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber and the second film forming chamber, respectively, and then the biaxially stretched nylon 6 film having a thickness of 15 μm is line speed. Electric power is applied while being conveyed at 200 m / min, and the first layer has a thickness of 60 mm and the second layer has a thickness of 70 mm on one corona-treated surface of a biaxially stretched nylon 6 film having a thickness of 15 μm. A barrier oxide film according to the present invention was produced by forming a two-layer silicon oxide layer having a thickness of 130 mm.

A biaxially stretched nylon 6 film having a thickness of 15 μm was prepared as a base film, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas and inert gas helium supplied from the gas supply device. The raw material gas was used.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is set to HMDSO: O ₂ : He = 1: 0: 1 (unit: slm, standard driter-minit), and the second As a raw material gas used in the film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He = 1: 10: 1 (unit: slm), and further, as a raw material gas used in the third film forming chamber The mixing ratio of the raw material gases was HMDSO: O ₂ : He = 1: 0: 1 (unit: slm).
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While conveying the biaxially stretched nylon 6 film at a line speed of 300 m / min, electric power was applied, and on the one corona-treated surface of the biaxially stretched nylon 6 film having a thickness of 15 μm, the thickness of the first layer was 40 mm, A barrier oxide film according to the present invention was manufactured by forming a three-layer silicon oxide layer having a thickness of 45 mm of the second layer, a thickness of 45 mm of the third layer, and a total thickness of 130 mm.

In the above Example 2, as a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is set to HMDSO: O ₂ : He = 1: 10: 1 (unit: slm, standard-driter-minute). In addition, as a source gas used in the second film forming chamber, the mixing ratio of the source gases is set to HMDSO: O ₂ : He = 1: 0: 1 (unit: slm). As the raw material gas used in the chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He = 1: 8: 1 (unit: slm), and the others are exactly the same as in Example 2 above, A barrier film according to the present invention similar to that of Example 2 was produced.

  In Example 2 above, tetramethoxysilane (hereinafter referred to as TMOS) is used in place of HMDSO, which is an organosilicon compound constituting the source gas, and the others are exactly the same as in Example 2 above. A barrier film according to the present invention similar to that of Example 2 was produced.

  In Example 2 above, tetraethoxysilane (hereinafter referred to as TEOS) is used instead of HMDSO, which is an organosilicon compound that constitutes the raw material gas, and the others are exactly the same as in Example 2 above. A barrier film according to the present invention similar to that of Example 2 was produced.

  In Example 2 above, tetramethoxysilane (hereinafter referred to as TMOS) is used in place of HMDSO, which is an organosilicon compound constituting the source gas in the second film forming chamber, and the others are the same as in the above Example. In the same manner as in Example 2, a barrier film according to the present invention similar to Example 2 was produced.

  In Example 2 described above, tetramethoxysilane (hereinafter referred to as TMOS) is used in place of HMDSO, which is an organosilicon compound constituting the source gas in the second film forming chamber, and the second film forming is performed. Tetraethoxysilane (hereinafter referred to as TEOS) is used in place of HMDSO, which is an organosilicon compound that constitutes the source gas in the chamber, and the others are exactly the same as in Example 2 above. The same barrier film according to the present invention was produced.

Plasma chemical vapor deposition apparatus in which biaxially stretched nylon 6 film having a thickness of 15 μm is prepared as a base film, and two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. Attached to.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas supplied from the gas supply device and helium, which is an inert gas, did.
Next, a raw material gas having a gas mixture ratio shown in Table 1 below is used, and the raw material gas is introduced into the first film forming chamber and the second film forming chamber from two supply pipes that can be independently controlled. Then, while the biaxially stretched nylon 6 film having a thickness of 15 μm is conveyed at a line speed of 200 m / min, electric power is applied, and one of the corona-treated surfaces of the biaxially stretched nylon 6 film having a thickness of 15 μm is applied. A barrier oxide film according to the present invention was manufactured by forming a two-layer silicon oxide layer having a thickness of 60 mm of the first layer, a thickness of 70 mm of the second layer, and a total thickness of 130 mm.

(Table 1)
┌───┬───────────────────────────┐┐ │ │ Supply pipe 1 of the first chamber │ │ ├────── ──────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├─────── ────┼───────────────┤ │ │ HMDSO │ 0.5: 5: 0.5 │ │ Room 1 ├────────── ─┴───────────────┤ │ │ Supply pipe 2 in the first chamber │ │ ├ ───────────┬───────── ───────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼─────────── ─────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴── ────────────┤ │ │ Supply pipe 1 of the second chamber │ │ ├ ───────────┬────────────── ──┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼──────────────── │ │ │ HMDSO │ 0.5: 5: 0.5 │ │ Room 2 ────────────┴───────────────┤ │ │ Supply pipe 2 of the second chamber │ │ ├ ───────────┬───────────────┤ │ │ Film forming monomer gas │ Gas mixing ratio (Unit: slm) │ │ ├ ───────────┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴───────────────┤ │Room 3│ Not used │ └───┴───────────────────────────┘

Plasma chemical vapor deposition apparatus in which biaxially stretched nylon 6 film having a thickness of 15 μm is prepared as a base film, and two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. Attached to.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas supplied from the gas supply device and helium, which is an inert gas, did.
Next, a raw material gas having a gas mixture ratio shown in Table 2 below is used, and the raw material gas is respectively supplied to the first film forming chamber, the second film forming chamber, and the third film forming chamber. Introduced from two supply pipes that can be controlled independently, then, while feeding the above-mentioned 15 μm-thick biaxially stretched nylon 6 film at a line speed of 300 m / min, power was applied to the biaxially stretched nylon 6 having a thickness of 15 μm. On one corona-treated surface of the film, a three-layer silicon oxide layer comprising a first layer thickness of 45 mm, a second layer thickness of 45 mm, a third layer thickness of 40 mm, and a total film thickness of 130 mm. A barrier film according to the present invention was produced by forming a film.

(Table 2)
┌───┬───────────────────────────┐┐ │ │ Supply pipe 1 of the first chamber │ │ ├────── ──────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├─────── ────┼───────────────┤ │ │ HMDSO │ 0.5: 5: 0.5 │ │ Room 1 ├────────── ─┴───────────────┤ │ │ Supply pipe 2 in the first chamber │ │ ├ ───────────┬───────── ───────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼─────────── ─────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴── ────────────┤ │ │ Supply pipe 1 of the second chamber │ │ ├ ───────────┬────────────── ──┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼──────────────── │ │ │ HMDSO │ 0.5: 5: 0.5 │ │ Room 2 ────────────┴───────────────┤ │ │ Supply pipe 2 of the second chamber │ │ ├ ───────────┬───────────────┤ │ │ Film forming monomer gas │ Gas mixing ratio (Unit: slm) │ │ ├ ───────────┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴───────────────┤ │ │ 3rd Supply pipe 1 │ │ ├───────────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├ ───────────┼───────────────┤ │ │ HMDSO │ 0.5: 5: 0.5 │ │Third Muroru───────────┴───────────────┤ │ │ Supply pipe 2 of the third chamber │ │ ├──────── ───┬───────────────┤ │ │ Film forming monomer gas │ Gas mixing ratio (unit: slm) │ │ ├ ─────────── ─┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ └───┴───────────┴─ ──────────────┘

Plasma chemical vapor deposition apparatus in which biaxially stretched nylon 6 film having a thickness of 15 μm is prepared as a base film, and two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. Attached to.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane) and TMOS (tetramethoxysilane) which are organic silicon compounds which are raw materials are volatilized in a raw material volatilization supply device, and oxygen gas and inert gas helium which are supplied from the gas supply device. And mixed to obtain a raw material gas.
Next, a raw material gas having a gas mixture ratio shown in Table 3 below is used, and the raw material gas is respectively supplied to the first film forming chamber, the second film forming chamber, and the third film forming chamber. It is introduced from two supply pipes that can be controlled independently, and then the above-mentioned biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is conveyed at a line speed of 300 m / min. On one corona-treated surface of a nylon 6 film, a three-layer silicon oxide layer having a first layer thickness of 40 mm, a second layer thickness of 45 mm, a third layer thickness of 45 mm, and a total thickness of 130 mm The barrier film according to the present invention was produced by forming a layer.

(Table 3)
┌───┬───────────────────────────┐┐ │ │ Supply pipe 1 of the first chamber │ │ ├────── ──────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├─────── ────┼───────────────┤ │ │ TMOS │ 0.5: 2.5: 0.5 │ │Room 1 ├──────── ───┴───────────────┤ │ │ Supply pipe 2 in the first chamber │ │ ├ ───────────┬─────── ─────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼───────── ───────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴─ ─────────────┤ │ │ Supply pipe 1 of the second chamber │ │ ├ ───────────┬───────────── ───┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼─────────────── ─┤ │ │ TMOS │ 0.5: 2.5: 0.5 │ │Room 2 ────────────┴─────────────── │ │ │ Supply pipe 2 of the second chamber │ │ ├───────────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├ ────────────┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0 .5 │ ├───┼───────────┴───────────────┤ │ │ Three-room supply pipe 1 │ │ ├ ───────────┬───────────────┤ │ │ Film-forming monomer gas │ Gas mixing ratio ( Unit: slm) │ │ ├ ├───────────┼───────────────┤┤ │ │ TMOS │ 0.5: 2.5: 0.5 │ │ Room 3 ├───────────┴───────────────┤ │ │ Supply pipe 2 of room 3 │ │ ├──── ───────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├────── ─────┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ └───┴───────── ──┴───────────────┘

Plasma chemical vapor deposition apparatus in which biaxially stretched nylon 6 film having a thickness of 15 μm is prepared as a base film, and two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. Attached to.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane), TMOS (tetramethoxysilane) and TEOS (tetraethoxysilane), which are organic silicon compounds as raw materials, are volatilized in a raw material volatilization supply device, and oxygen gas supplied from the gas supply device The raw material gas was mixed with helium, which is an inert gas.
Next, a raw material gas having a gas mixing ratio shown in Table 4 below is used, and the raw material gas is respectively supplied to the first film forming chamber, the second film forming chamber, and the third film forming chamber. Introduced from two supply pipes that can be controlled independently, then, while feeding the above-mentioned 15 μm-thick biaxially stretched nylon 6 film at a line speed of 300 m / min, power was applied to the biaxially stretched nylon 6 having a thickness of 15 μm. On one corona-treated surface of the film, a three-layer silicon oxide layer comprising a first layer thickness of 45 mm, a second layer thickness of 45 mm, a third layer thickness of 40 mm, and a total film thickness of 130 mm. A barrier film according to the present invention was produced by forming a film.

(Table 4)
┌───┬───────────────────────────┐┐ │ │ Supply pipe 1 of the first chamber │ │ ├────── ──────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├─────── ────┼───────────────┤ │ │ TMOS │ 0.5: 2.5: 0.5 │ │Room 1 ├──────── ───┴───────────────┤ │ │ Supply pipe 2 in the first chamber │ │ ├ ───────────┬─────── ─────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼───────── ───────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ ├───┼───────────┴─ ─────────────┤ │ │ Supply pipe 1 of the second chamber │ │ ├ ───────────┬───────────── ───┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├───────────┼─────────────── ─┤ │ │ TEOS │ 0.5: 2.5: 0.5 │ │ Room 2 ├───────────┴─────────────── │ │ │ Supply pipe 2 of the second chamber │ │ ├───────────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit: slm) │ │ ├ ───────────┼───────────────┤ │ │ TEOS │ 0.5: 0: 0 .5 │ ├───┼───────────┴───────────────┤ │ │ Supply pipe 1 │ │ ├ ───────────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixing ratio (unit : Slm) │ │ ├ ───────────┼───────────────┤ │ │ TMOS │ 0.5: 2.5: 0.5 │ │Room 3 ├───────────┴───────────────┤ │ │ Supply pipe 2 of room 3 │ │ ├───── ──────┬───────────────┤ │ │ Monomer gas for film formation │ Gas mixture ratio (unit: slm) │ │ ├─────── ────┼───────────────┤ │ │ HMDSO │ 0.5: 0: 0.5 │ └───┴────────── ─┴───────────────┘

  In Example 2 described above, instead of using a biaxially stretched nylon 6 film having a thickness of 15 μm as the base film, a resin composition containing a thermosetting acrylic resin as a main component of the vehicle on one surface thereof Is coated by a kiss roll coating method and then dried to form a coating film having a thickness of 1 μm and a biaxially stretched nylon 6 film having a thickness of 15 μm is used. In the same manner as in Example 2, a barrier film according to the present invention was produced in the same manner as in Example 2 above.

  In Example 9 above, instead of using a biaxially stretched nylon 6 film having a thickness of 15 μm as the base film, a thermosetting acrylic resin is used as the main component of the vehicle on one side of the base film. A biaxially stretched nylon 6 film having a thickness of 15 μm formed by coating a resin composition is made by a kiss roll coating method and then dried to form a coating film having a thickness of 1 μm. Produced a barrier film according to the present invention in the same manner as in Example 9 described above.

(Comparative Example 1)
A biaxially stretched nylon 6 film having a thickness of 15 μm was prepared as a base film, and this was mounted on a plasma chemical vapor deposition apparatus having three chambers as shown in FIG.
Next, the pressure in the chamber of the plasma chemical vapor deposition apparatus was reduced.
On the other hand, HMDSO (hexamethyldisiloxane), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device and mixed with oxygen gas supplied from the gas supply device and helium, which is an inert gas, did.
As a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases was set to HMDSO: O ₂ : He = 1: 10: 1 (unit: slm, standard-driter-minit).
The second film forming chamber and the third film forming chamber were not used.
Using the raw material gas as described above, each of the raw material gases is introduced into the first film forming chamber, and then the above-mentioned biaxially stretched nylon 6 film having a thickness of 15 μm is conveyed at a line speed of 100 m / min. Electric power was applied to form a single silicon oxide layer having a thickness of 130 mm on one corona-treated surface of a biaxially stretched nylon 6 film having a thickness of 15 μm to produce a barrier film.

(Comparative Example 2)
In Comparative Example 1 above, instead of using HMDSO (hexamethyldisiloxane), which is an organosilicon compound, as the source gas, TMOS (tetramethoxysilane), which is an organosilicon compound, is used. In the same manner as in Example 1, a barrier film was produced in the same manner as in Comparative Example 1 above.

(Comparative Example 3)
In Comparative Example 1 above, instead of using HMDSO (hexamethyldisiloxane), which is an organosilicon compound, as the source gas, TEOS (tetraethoxysilane), which is an organosilicon compound, is used. In the same manner as in Example 1, a barrier film was produced in the same manner as in Comparative Example 1 above.

(Comparative Example 4)
In the first embodiment, as the raw material gas used in the first film forming chamber, the mixing ratio of the raw material gas is HMDSO: O ₂ : He = 1: 0: 1 (unit: slm, standard-driter-minit) In addition, as a raw material gas used in the second film forming chamber, instead of setting the mixing ratio of the raw material gases to HMDSO: O ₂ : He = 1: 10: 1 (unit: slm), As a raw material gas used in the film forming chamber and a raw material gas used in the second film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He = 1: 10: 1 (unit: slm) Other than that, a barrier film was produced in the same manner as in Example 1 in exactly the same manner as in Example 1 above.

(Comparative Example 5)
In the above Example 2, as a raw material gas used in the first film forming chamber, the mixing ratio of the raw material gases is HMDSO: O ₂ : He = 1: 0: 1 (unit: slm, standard-driter-minit) In addition, as a source gas used in the second film-forming chamber, the mixing ratio of the source gases is set to HMDSO: O ₂ : He = 1: 10: 1 (unit: slm). As a raw material gas used in the chamber, a raw material gas used in the first film forming chamber instead of setting the mixing ratio of the raw material gases to HMDSO: O ₂ : He = 1: 0: 1 (unit: slm) , HMDSO: O ₂ : He = 1: 10: 1 (unit: source gas used in the second film forming chamber and source gas used in the third film forming chamber) Slm), and the others are exactly the same as in Example 2 above, As in Example 2, was prepared barrier film.

(Comparative Example 6)
In the above Comparative Example 1, instead of using a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm as a base film, a thermosetting acrylic resin is used as a base film on one side of the vehicle. Using a biaxially stretched nylon 6 film having a thickness of 15 μm, a resin composition having a main component is coated by a kiss roll coating method and then dried to form a coating film having a thickness of 1 μm. Other than that, a barrier film was produced in the same manner as in Comparative Example 1 in the same manner as in Comparative Example 1 above.

(Experimental example 1)
For the barrier films produced in Examples 1 to 13 and Comparative Examples 1 to 6, oxygen permeability and water vapor permeability were measured.
(1). Measurement of Oxygen Permeability This is for a barrier film under the conditions of a temperature of 23 ° C. and a humidity of 90% RH on a measuring instrument manufactured by Mocon, USA [model name, OX-TRAN 2/20]. Measured.
(2). Measurement of water vapor permeability This is for a barrier film under the conditions of a temperature of 40 ° C. and a humidity of 90% RH on a measuring instrument manufactured by Mocon, USA [model name, Permatran 3/31]. Measured.
The measurement results are shown in Table 5 below.

(Table 5)
┌─────┬────────────────┐ │ │ Barrier film │ │ ├───────┬────────┤ │ Oxygen permeability │ Water vapor permeability │ ├─────┼───────┼────────┤ │Example 1 │ 1.8 │ 6.7 │ ├─── ──┼───────┼────────┤ │Example 2 │ 1.3 │ 4.9 │ ├─────┼───────┼── ──────┤ │Example 3 │ 1.1 │ 5.4 │ ├─────┼───────┼────────┤ │Example 4 │ 0 │ 7.5 │ ├─────┼───────┼────────┤ │Example 5 │ 1.3 │ 6.8 │ ├───── ┼───────┼────────┤ │Example 6 │ 0.6 │ 5.5 │ ├─────┼───────┼─── ─────┤ │Example 7 │ 0.7 │ 5.2 │ ├─────┼───────┼────────┤ │Example 8 │ 0. 8 │ 5.8 │ ├─────┼───────┼────────┤ │Example 9 │ 0.9 │ 6.1 │ ├─────┼ ───────┼────────┤ │Example 10│ 0.7 │ 5.4 │ ├─────┼───────┼───── ───┤ │Example 11│ 0.5 │ 4.8 │ ├─────┼───────┼────────┤ │Example 12│ 1.5 │ 4.4 │ ├─────┼───────┼────────┤ │Example 13│ 0.9 │ 5.8 │ ├─────┼── ─────┼────────┤ │Comparative Example 1 │ 3.2 │ 13.1 │ ├─────┼───────┼──────── ─┤ Comparative Example 2 │ 2.7 │ 18.9 │ ├─────┼───────┼────────┤ │ Comparative Example 3 │ 3.0 │ 15.2 │ ├ ─────┼───────┼────────┤ │Comparison 4 │ 2.0 │ 8.4 │ ├───────────── ┼────────┤ │Comparative Example 5 │ 1.9 │ 8.2 │ ├─────┼───────┼────────┤ │Comparative Example 6 │ 3.2 │ 12.8 │ └─────┴───────┴────────┘ In Table 5 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. · 90% RH].

  As is clear from the results shown in Table 5 above, the barrier film according to the present invention was excellent in oxygen permeability and water vapor permeability.

(Experimental example 2)
About the barrier film manufactured in said Examples 1-13 and Comparative Examples 1-6, the glow discharge plasma generator is used for the surface of the outermost silicon oxide layer which comprises the barrier layer. , Power 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: slm) mixed gas pressure 6 × 10 ⁻⁵ Torr, processing speed Oxygen / argon mixed gas plasma treatment was performed at 420 m / min to form a plasma treated surface in which the surface tension of the silicon oxide layer was improved by 54 dyne / cm or more.
Next, an epoxy-based silane coupling agent (8.0 wt%) and an anti-blocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the plasma-treated surface formed above. Then, a primer composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). An agent layer was formed.
Further, a two-component curing type polyurethane laminating adhesive is used on the surface of the primer layer formed as described above, and this is applied to a film thickness of 4.0 g / m ² (by gravure roll coating method). The adhesive layer for laminating was formed by coating so as to be in a dry state.
Next, on the surface of the laminating adhesive layer formed as described above, a linear low density polyethylene film having a thickness of 50 μm is overlapped with its corona-treated surface facing each other, and then both are laminated with dry laminating. The laminated material was manufactured by laminating.
Next, the oxygen permeability and water vapor permeability of the above laminated material were measured in the same manner as in Experimental Example 1.
(1). Measurement of Oxygen Permeability This is for a laminated material under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, using a measuring instrument manufactured by Mocon, USA (model name: OX-TRAN 2/20). It was measured.
(2). Measurement of water vapor transmission rate This is the measurement of the laminate material under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, manufactured by MOCON, USA [model name, PERMATRAN 3/31]. It was measured.
The measurement results are shown in Table 6 below.

(Table 6)
┌─────┬────────────────┐ │ │ Layered material │ │ ├───────┬────────┤ │ │ Oxygen permeability │ Water vapor permeability │ ├─────┼───────┼────────┤ │Example 1 │ 1.6 │ 2.3 │ ├─── ──┼───────┼────────┤ │Example 2 │ 1.3 │ 1.5 │ ├─────┼───────┼── ──────┤ │Example 3 │ 0.9 │ 1.9 │ ├─────┼───────┼────────┤ │Example 4 │ 0 │ 2.1 │ ├─────┼───────┼────────┤ │Example 5 │ 1.3 │ 2.3 │ ├ ────── ┼───────┼────────┤ │Example 6 │ 0.5 │ 1.6 │ ├─────┼───────┼──── ─── ││Example 7 │ 0.6 │ 1.5 │ ├─────┼───────┼────────┤ │Example 8 │ 0.7 │ 1.7 │ ├─────┼───────┼────────┤ │Example 9 │ 0.8 │ 1.9 │ ├─────┼───── ──┼────────┤ │Example 10│ 0.6 │ 1.8 │ ├────┼┼───────┼────────┤ │ Example 11│ 0.5 │ 1.5 │ ├─────┼───────┼────────┤ │Example 12│ 1.3 │ 1.4 │ ├ ─────┼───────┼────────┤ │Example 13│ 0.8 │ 1.6 │ ├─────┼─────── ┼────────┤ │Comparative Example 1 │ 3.0 │ 5.6 │ ├─────┼───────┼────────┤ │Comparative Example 2 2.5 │ 7.9 │ ├─────┼───────┼────────┤ │Comparative Example 3 │ 3.0 │ 7.5 │ ├──── ─┼───────┼────────┤ │Comparative Example 4 │ 1.6 │ 2.5 │ ├─────┼───────┼─── ─────┤ │Comparative Example 5 │ 1.2 │ 2.2 │ ├─────┼───────┼────────┤ │Comparative Example 6 │３. 0 │ 5.4 │ └─────┴───────┴─────────┘ In Table 6 above, the unit of oxygen permeability is [cc / m ² / day The unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90% RH].

  As is clear from the results shown in Table 6 above, the laminated material using the barrier film according to the present invention was excellent in oxygen permeability and water vapor permeability.

(Experimental example 3)
About the barrier film manufactured in said Example 2 and Comparative Example 1, the change of the structural component of the depth direction of the silicon oxide layer which comprises the barrier layer was measured.
This is because the barrier film is subjected to elemental analysis in the depth direction from the film surface of the silicon oxide layer using an X-ray photoelectron spectroscopy (XPS), and silicon, oxygen detected at that time are analyzed. And, the amount of carbon was measured and evaluated.
The results are shown in Table 7 below.
Moreover, about the barrier film, the IR absorption peak position based on Si—O—Si stretching vibration and the IR absorption peak strength based on Si—CH ₃ stretching vibration were measured.
This is a free-transform infrared spectrophotometer (manufactured by JASCO Corporation, model name, Herschel FT / IR) equipped with a multiple reflection measuring device (manufactured by JASCO Corporation, model name, ATR-300 / H). -610).
The infrared absorption spectrum was measured at an incident angle of 45 degrees using a germanium crystal as a prism.
The results are shown in Table 7 below.

(Table 7)
┌───────┬──────────┬─────────┬──────┐ │ │ Si: O: C │Si-O-Si Pi-Si-CH ₃ │ │ │ │Position [cm ^-1 ] │ Absorption strength │ ├─┬─────┼──────────┼───────── ─┼──────┤ │Real │1 layer │ │ │ │ │ │ (surface) │100: 160: 90│1038 │0.028 │ │Example ├─────┼─── ───────┼─────────┼──────┤ │2│2 layers │100: 185: 13│ 1065 │0.010 │ │ │──── ─┼──────────┼─────────┼──────┤ │ │3 layers │ │ │ │ │ │ (base material side) │100: 170 : 85│ 1040 │0.027 │ ├─┼─────┼──────────┼─ ───────┼──────┤ │ Ratio │1 layer │ │ │ │ │Comparison (surface) │100: 180: 17│ 1060 │0.012 │ │Example ├─── ──┼──────────┼─────────┼──────┤ │1│2 layers │100: 185: 15│ 1065 │0.011 │ │ ├─────┼──────────┼─────────┼──────┤ │ │3 layers │ │ │ │ │ │ (base material Side) │100: 188: 15│1065 │0.012 │ └─┴─────┴──────────┴─────────┴────── ─┘

From the results shown in Table 7 above, regarding the barrier film produced in Example 2 and Comparative Example 1, the change in the constituent components in the depth direction of the silicon oxide layer constituting the barrier layer, and The IR absorption peak position based on the Si—O—Si stretching vibration and the IR absorption peak intensity based on the Si—CH ₃ stretching vibration were as described above.

(Experimental example 4)
Using the laminated material manufactured in the above Experimental Example 2, the surfaces of the linear low density polyethylene film having a thickness of 50 μm are opposed to each other, and then the end portions around the outer periphery of the three sides are heat sealed. A three-sided sealing type packaging bag was manufactured, and then the dressing was filled from the opening of the packaging bag, and then the opening was heat sealed to manufacture a packaged product.
Next, the packaged product was stored in an oven at 40 ° C., and whether or not there was an odor on the surface of the laminated material was examined by human senses, and the fragrance retention was measured.
When the smell did not leak at all, it was marked with ◯, when it smelled faint, it was marked with △, and when it smelled quite a bit, it was marked with ×.
The results are shown in Table 8 below.

(Table 8)
┌ ─────┬───────┐ │ │ Aroma │ ├─────┼───────┤ │Example 1 │ ○ │ ├─────┼ ───────┤ │Example 2 │ ○ │ ├─────┼───────┤ │Example 3 │ ○ │ ├─────┼────── ─┤ │Example 4 │ ○ │ ├────┼───────┤ │Example 5 │ ○ │ ├─────┼───────┤ │Example 6 │ ○ │ ├─────┼───────┤ │Example 7 │ ○ │ ├─────┼───────┤ │Example 8 │ ○ │ ├── ───┼───────┤ │Example 9 │ ○ │ ├─────┼───────┤ │Example 10│ ○ │ ├ ─────┼── ─────┤ │Example 11│ ○ │ ├─────┼───────┤ │Example 12│ ○ │ ├────┼───── ──┤ │Example 13│ ○ │ ├ ───┼───────┤ │Comparative Example 1 │ × │ ├─────┼───────┤ │Comparative Example 2 │ × │ ├─────┼───────┤ │Comparative Example 3 │ × │ ├─────┼───────┤ │Comparative Example 4 │ △ │ ├─ ────┼───────┤ │Comparative Example 5 │ △ │ ├─────┼──────┤ │Comparative Example 6 │ △ │ └─────┴─ ──────┘

  As is clear from the results shown in Table 8 above, the laminated material using the barrier film according to the present invention was excellent in fragrance retention.

  The barrier film according to the present invention is excellent in adhesion between a base material film made of a polyamide-based resin film and a silicon oxide layer, and the silicon oxide layer has excellent ductility, flexibility, flexibility, and the like. Excellent, without cracks, etc., and has a high barrier property that can completely block the transmission of oxygen gas, water vapor, etc., for example, as a barrier material used for packaging materials, etc. It is excellent in gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like, and an extremely useful barrier film that does not show a decrease in performance of the gas barrier properties can be produced.

It is a schematic block diagram which shows the schematic structure of an example of the manufacturing apparatus about the barrier film concerning this invention. It is a schematic block diagram which shows the schematic structure of an example of the manufacturing apparatus about the barrier film concerning this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film concerning this invention.

Explanation of symbols

A barrier film 41 base film made of polyamide resin film 42 barrier layer 42a silicon oxide layer 42b silicon oxide layer 42c silicon oxide layer

Claims (11)

A polyamide resin film;
It consists of a barrier layer provided on one side of the polyamide resin film,
Further, the barrier layer uses at least two film forming chambers, and for each chamber, a film forming monomer gas consisting of at least one organic silicon compound, oxygen gas, and Use two or more film-forming mixed gas compositions prepared by changing the mixing ratio of each gas component of the film-forming mixed gas composition containing an inert gas, and use each film-forming mixed gas composition And two or more layers of silicon oxide layers formed by plasma enhanced chemical vapor deposition,
Furthermore, respective silicon oxide layer contains carbon atoms in its film, and Ri Do different carbon content for each silicon oxide layer, furthermore, from the film surface carbon content of the film A barrier film characterized by increasing in the depth direction . 2. The barrier film according to claim 1, wherein the polyamide resin film is a biaxially stretched polyamide resin film. Organosilicon compounds are 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenyl The above-mentioned, characterized by comprising one or more of silane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, or octamethylcyclotetrasiloxane The barrier film as described in any one of Claims 1-2. The barrier film according to any one of claims 1 to 3, wherein the inert gas is argon gas or helium gas. 1 is a gas mixture of a gas composition monomer gas: oxygen gas: inert gas = 1: 0 to 5: 1 (unit: slm, abbreviation of standard-driter-minit). It consists of composition ratios, The barrier film as described in any one of said Claims 1-4 characterized by the above-mentioned. The film forming mixed gas composition 2 is a gas of monomer gas for film formation: oxygen gas: inert gas = 1: 6 to 15: 1 (unit: slm, abbreviation of standard-driter-minit). It consists of composition ratios, The barrier film as described in any one of said Claims 1-5 characterized by the above-mentioned. The silicon oxide layer has a component ratio of 150 to 200 O atoms and 50 to 100 C atoms with respect to 100 Si atoms, and further Si—O—Si stretching vibration between 1030 cm ^{−1 to} 1060 cm ^−1. 6. The barrier film according to claim 5, wherein the barrier film has IR absorption based on the above and IR absorption based on Si—CH 3 stretching vibration at 1274 ± 4 cm ⁻¹ . The silicon oxide layer has a component ratio of 150 to 200 O atoms and 50 or less C atoms to 100 Si atoms, and further exhibits Si—O—Si stretching vibration between 1045 cm ^{−1 to} 1075 cm ^−1. The barrier film according to claim 6, wherein the barrier film has IR absorption based on IR absorption based on Si—CH 3 stretching vibration at 1274 ± 4 cm ⁻¹ . The silicon oxide layer is a silicon oxide layer prepared by forming a first layer with a thickness of 30 to 300 mm and a second layer with a thickness of 30 to 300 mm, or a first layer with a thickness of 20 to 200 mm, a second layer. The barrier film according to any one of claims 1 to 8, which comprises a silicon oxide layer formed by preparing a film of 20 to 200 mm and a third layer of 20 to 200 mm. The barrier film according to any one of claims 1 to 9 , wherein the plasma chemical vapor deposition method comprises a low temperature plasma chemical vapor deposition method. Silicon oxide on a polyamide resin film supply chamber, a first film forming chamber, a second film forming chamber, a third film forming chamber, and a polyamide resin film as a base film Using a plasma chemical vapor deposition apparatus with a basic structure consisting of a winding chamber that winds up a barrier film that has been layered and layered,
First, the polyamide resin film wound around the unwinding roll is unwound to the first film forming chamber,
Next, the polyamide-based resin film is conveyed on the cooling / electrode drum peripheral surface at a predetermined speed via an auxiliary roll,
Next, from the raw material volatilization supply apparatus and the gas supply apparatus, a film forming monomer gas, oxygen gas, and inert gas composed of one or more organic silicon compounds are used, and the mixing ratio of the gas components composed of them. The mixed gas composition for film formation is supplied while preparing the above, and the mixed gas composition for film formation is introduced into the first film formation chamber through the raw material supply nozzle,
Then, a plasma is generated by glow discharge plasma on the polyamide-based resin film transported on the cooling / electrode drum peripheral surface, and irradiated with this to form a second silicon oxide containing silicon oxide. One silicon oxide layer is formed,
Next, the polyamide-based resin film obtained by forming the first silicon oxide layer in the first film forming chamber is fed out to the second film forming chamber through an auxiliary roll.
Next, in the same manner as described above, the polyamide-based resin film obtained by forming the first silicon oxide layer is transported to the cooling / electrode drum peripheral surface at a predetermined speed.
Thereafter, in the same manner as described above, from the raw material volatilization supply device and the gas supply device, a film-forming monomer gas, oxygen gas, and inert gas composed of one or more organic silicon compounds are used. The film-forming mixed gas composition is supplied while adjusting the mixing ratio of the gas components, and the film-forming mixed gas composition is introduced into the second film-forming chamber through the raw material supply nozzle,
Then, on the first silicon oxide layer of the polyamide-based resin film obtained by forming the first silicon oxide layer transported on the cooling / electrode drum peripheral surface, the glow discharge plasma is used. Plasma is generated and irradiated to form a second silicon oxide layer made of silicon oxide containing carbon atoms,
Further, in the same manner as described above, a polyamide-based resin film in which the first and second silicon oxide layers are formed in the second film-forming chamber is supplied to the third product through an auxiliary roll. It goes out to the membrane room,
Next, in the same manner as described above, the polyamide-based resin film in which the first and second silicon oxide layers are formed is transported at a predetermined speed onto the circumferential surface of the cooling and electrode drum
Thereafter, in the same manner as described above, from the raw material volatilization supply device and the gas supply device, a film-forming monomer gas, oxygen gas, and inert gas composed of one or more organic silicon compounds are used. The film-forming mixed gas composition is supplied while adjusting the mixing ratio of the gas components, and the film-forming mixed gas composition is introduced into the third film-forming chamber through the raw material supply nozzle,
Then, on the second silicon oxide layer of the polyamide resin film formed by forming the first and second silicon oxide layers conveyed on the cooling / electrode drum peripheral surface, -Plasma is generated by discharge plasma and irradiated to form a third silicon oxide layer made of silicon oxide containing carbon atoms,
Next, the silicon oxide layers of the first layer, the second layer, and the third layer are formed as described above, and the polyamide-based resin film in which these layers are stacked is fed out to the take-up chamber through the auxiliary roll. A barrier film in which the first layer, the second layer, and the third silicon oxide layer are stacked is wound on a winding roll.
A method for producing a barrier film characterized by the following.

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