JP2005103870A - Laminated material and small bag for packaging liquid using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a useful small bag for packaging a liquid formed using a laminated material using a barrier film excellent in gas barrier properties for preventing the permeation of an oxygen gas, steam or the like, not causing the leak of a smell or the like even if a dressing, soy sauce, sauce, mayonnaise, Miso, vinegar and other seasonings are subjected to hot filling packaging and extremely excellent in aroma retaining properties or the like. <P>SOLUTION: This laminated material is composed of a polyamide resin film and the barrier layer provided to one side surface thereof. The barrier layer is constituted by providing at least a coating film comprising a polyurethane resin composition or a polyester resin composition on the barrier layer of a barrier film comprising at least two silicon oxide layers by a plasma chemical vapor phase growth method and further providing a heat-sealable resin layer thereon through an adhesive layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminated material and a liquid-filled packaging pouch using the same.

  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.

  The present inventor also has a base material and a barrier layer provided on at least one surface of the base material, and the barrier layer is made of silicon oxide, and includes carbon, hydrogen, silicon and The present invention proposes a barrier film characterized by being a continuous layer containing at least one compound composed of one kind of oxygen or two or more kinds of elements, and a method for producing the same (for example, (See Patent Document 1).

  Further, the present inventor has provided 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 The laminated body used is also proposed (for example, refer patent document 2).

  In addition, the inventor of the present invention provides an inorganic oxide film on one surface of a biaxially stretched nylon film, and further includes a silane coupling agent and a filler on the inorganic oxide film. A transparent barrier film provided with a coating thin film made of a resin composition, a laminated material obtained by laminating the transparent barrier film, and a packaging container are proposed (for example, see Patent Document 3).

Furthermore, the present inventor provided at least two layers of inorganic oxide thin films on one surface of the nylon film, and further includes a silane coupling agent on the inorganic oxide thin film. A laminated material comprising: a coating thin film made of a primer composition or a polyester resin composition; and at least a heat-sealable resin layer laminated on the coating thin film; A packaging container using the same is also proposed (for example, see Patent Document 4).
JP-A-8-142252 (Claims etc.) Japanese Patent Laid-Open No. 11-348171 (Claims etc.) JP 2000-167972 A (Claims etc.) JP 2000-233468 A (Claims etc.)

  However, in the invention according to the above patent document, it has a high gas barrier property that prevents permeation of oxygen gas, water vapor, etc., and is excellent in transparency, flexibility, flexibility, impact resistance, etc. Although it is possible to produce a barrier film having the advantage of having range suitability, it can be used as a barrier material, and another substrate can be arbitrarily laminated thereon to produce a packaging material. Thereafter, the packaging material is made into a bag to produce a desired packaging bag, and thus, for example, dressing, soy sauce, sauce, mayonnaise, miso, vinegar in the packaging bag. When a packaged product is manufactured by hot-packaging and packaging with other liquid seasonings, etc., there is a problem that odor leaks from the packaged product, and there is a problem that remarkably lacking in aroma retention, and any barrier film is used. Even if you want to To a circumstances because not a state capable of satisfying yet sufficiently.

  In particular, the inventions according to Patent Documents 2 and 4 described above are intended to improve the inventions according to Patent Documents 1 and 2, which include two or more inorganic oxide vapor deposited films formed by plasma chemical vapor deposition. However, the inorganic oxide vapor deposition films constituting the two layers form a thin film having substantially the same composition, configuration, etc., and the thin films are simply double-layered. Therefore, oxygen gas, water vapor, etc. that permeate the inorganic oxide vapor deposition film constituting one layer easily pass through the inorganic oxide vapor deposition film that constitutes the other one layer. It is far from blocking, and it is therefore extremely 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 can prevent permeation, for example, for packaging that constitutes a packaging bag for hot filling and packaging liquid seasonings such as dressing, soy sauce, sauce, mayonnaise, miso, vinegar, etc. When used as a material, there are problems such as leakage of odors and lack of scent retention, and in the case of any barrier film, the situation is still not fully satisfactory. It is.

  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. It is extremely useful in that it does not contain foreign matter, dust, etc. that cause cracks, and has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and no deterioration in performance of the gas barrier properties is observed. Manufacture a barrier film, and thus a laminated material using the same, and further make a bag of the laminated material. For example, dressing, soy sauce, sauce, mayonnaise, miso, vinegar, etc. It is intended to provide a useful pouch for liquid-filled packaging that does not cause odor leakage even when hot-packed with a liquid seasoning such as the above, and that is extremely excellent in fragrance retention.

  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, a barrier film having a different carbon atom content is produced for each silicon oxide layer, and thus the barrier film is used as a barrier material, and another substrate is used for this. A laminated material is optionally laminated to produce a laminated material, and then the laminated material is made into a bag to produce a packaging bag. In the packaging bag, for example, dressing, soy sauce, sauce, mayonnaise, When a packaged product is manufactured by hot-filling and packaging liquid seasonings such as miso, vinegar and others, a silicon-based oxide film is laminated by plasma chemical vapor deposition, The silicon oxide layer is excellent in adhesion with the silicon oxide layer, and the silicon oxide layer is excellent in spreadability, flexibility, flexibility, etc. It can be formed into a film and has at least two chambers. Two or more silicon oxide layers are continuously stacked using a plasma chemical vapor deposition apparatus comprising a film forming chamber, and each layer forms a film having high barrier properties. Therefore, it is possible to obtain a gas barrier property higher than that of a single layer, and further, by forming a film continuously to open to the atmosphere, foreign matter, dust, etc. that cause cracks are formed between the film forming layers. Further, each silicon oxide layer contains carbon atoms in the film, and each silicon oxide layer contains no carbon atoms. Since it is a discontinuous layer in which the carbon atom content is different every time, it is possible to completely prevent permeation of oxygen gas, water vapor, etc., for example, as a barrier material used for packaging materials, etc. Prevents permeation of oxygen gas, water vapor, etc. It is possible to produce a very useful barrier film that is excellent in gas barrier properties and has no decline in performance of the gas barrier properties, and further made a bag using a laminated material that uses this as a barrier material. Packaging bags, for example, do not leak odors and are highly fragrant even when hot-packed with liquid seasonings such as dressing, soy sauce, sauce, mayonnaise, miso, vinegar, etc. The present invention has been completed by finding that a useful liquid-filled packaging sachet excellent in the above can be produced.

  That is, the present invention comprises a polyamide resin film and a barrier layer provided on one surface of the polyamide resin film, and the barrier layer uses at least two film forming chambers. Further, for each chamber, mixing of each gas component of a film-forming mixed gas composition containing at least one kind of organic silicon compound, a gas-forming monomer gas, an oxygen gas, and an inert gas. Two or more layers of a mixed gas composition for film formation prepared by changing the ratio, and silicon oxide by plasma chemical vapor deposition of two or more layers formed using each of the mixed gas compositions for film formation Each of the silicon oxide layers contains carbon atoms in the film, and the content of the carbon atoms is different for each silicon oxide layer. On the sex layer at least A coating film made of a polyurethane-based resin composition or a polyester-based resin composition containing a ring agent and a filler is provided. Further, a heat seal is formed on the coating film via an adhesive layer. The present invention relates to a laminated material provided with a conductive resin layer and a liquid-filled packaging pouch using the same.

  A laminated material according to the present invention and a liquid-filled packaging pouch using the laminated material are obtained by laminating a silicon oxide layer by a plasma chemical vapor deposition method, thereby forming a polyamide-based resin film and a silicon oxide layer as a base film. The silicon oxide layer is excellent in spreadability, flexibility, flexibility, etc., and can be formed into a film having excellent excellent barrier properties from the first layer. In addition, two or more silicon oxide layers are continuously laminated using a plasma chemical vapor deposition apparatus composed of at least two film forming chambers, and each layer has a high barrier property. Since it is possible to form a film having a film, it is possible to obtain a gas barrier property higher than that of a single layer, and to cause cracks by continuously forming a film that opens to the atmosphere. Foreign matter, dust Can be prevented from being mixed between the film forming layers, and the barrier property is not lowered, and each silicon oxide layer contains carbon atoms in the film, and Since it is a discontinuous layer having a different carbon atom content for each silicon oxide layer, it is possible to completely prevent permeation of oxygen gas, water vapor, etc., for example, a barrier used for packaging materials, etc. As an active material, it is possible to produce a very useful barrier film that has excellent gas barrier properties that prevent permeation of oxygen gas, water vapor, etc., and no deterioration in the performance of the gas barrier properties is observed. Packaging bags made using the laminated material used as a raw material, for example, hot filling and packaging liquid seasonings such as dressing, soy sauce, sauce, mayonnaise, miso, vinegar, etc. Odor leak etc. Does not occur, is that is very excellent in aroma retention and the like.

  The laminated material according to the present invention and the liquid-filled packaging pouch using the same will be described in more detail below with reference to the drawings.

  FIG. 1 and FIG. 2 are schematic configuration diagrams showing a schematic configuration of one example of a manufacturing apparatus for a barrier film constituting a laminated material according to the present invention and a liquid-filled packaging sachet using the same, FIG. 3 is a schematic cross-sectional view showing an example of the layer structure of the barrier film according to the present invention manufactured using the barrier film manufacturing apparatus shown in FIGS. 1 and 2, and FIG. FIG. 5 is a schematic cross-sectional view showing an example of the layer structure of the laminated material according to the present invention manufactured using the barrier film shown in FIG. 3, and FIG. 5 is a bag making using the laminated material shown in FIG. FIG. 6 is a schematic perspective view showing an example of the liquid-filled packaging sachet according to the present invention, and FIG. 6 is produced by filling and packaging the contents in the liquid-filled packaging sachet shown in FIG. For packaging products according to the present invention Is a schematic perspective view showing an example in this household.

  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 other 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 mixed gas composition for film formation in the first and third film formation chambers (two chambers), the silicon oxide has high flexibility and high barrier property against water vapor. A film having a high barrier property against oxygen can be obtained by using the second mixed gas composition for film formation in the second film forming chamber. It is obtained.

  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. 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 a CH ₃ site, 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. It 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, IR absorption based on Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 There is a feature.

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. 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, cellulose resin such as ethyloxyethylcellulose, rubber-based resin such as chlorinated rubber, cyclized rubber, 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.

  Conventionally, generally, a polyamide-based resin film is excellent in puncture resistance, pinhole resistance, etc., and has a characteristic that it can be used as a packaging material for filling and packaging contents such as water. However, there is a drawback that water absorption is high and the barrier property is inferior, and until now, when filling and packaging a liquid as the contents, the weight reduction amount of the contents could not be used greatly. is there.

  Thus, in the present invention, a polyamide-based resin film is used as the base film, and even if the content is a liquid, it can be filled and packaged. Can be used.

  That is, in the present invention, a polyamide-based resin film is used as the base film, and by contrast, by stacking a plurality of silicon oxide layers as described above, it is excellent in puncture resistance, pinhole resistance, etc. In addition, it has a high barrier property against water vapor, oxygen, etc., in particular, has a high barrier property against water vapor, and is excellent in aroma retaining property, etc., and can produce a high barrier polyamide resin film. It is extremely useful as a packaging material as a base material.

  As apparent from the above description, 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-based film as shown in FIG. And a barrier layer 42 provided on one surface of a base film 41 made of resin. Further, the barrier layer 42 uses at least two film forming chambers, and each film forming chamber In addition, it was 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. Two or more film-forming mixed gas compositions were used, and two or more silicon oxide layers 42a, 42b, 42c formed by plasma chemical vapor deposition using the respective film-forming mixed gas compositions. Each of the silicon oxides 42a, 42b, and 42c contain silicon oxide as a main component, contain at least one compound composed of one or more elements of carbon, hydrogen, silicon, and oxygen, and each silicon oxide The barrier film A is characterized in that each of the 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 contains carbon base paper in the film, and each silicon oxide layer has the above-mentioned value. Since these are discontinuous layers having different carbon atom contents, they have various advantages in that permeation of oxygen gas, water vapor and the like can be completely prevented.

  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 The laminate according to the present invention having various forms can be produced by arbitrarily laminating one or more kinds of various base materials such as cloth or non-woven fabric, glass plate, etc. The laminated material is 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, or aluminum packaging material, It can be applied to various uses such as others.

  If the layer structure of the laminated material according to the present invention is specifically exemplified, as shown in FIG. 4, for example, silicon oxide for forming the barrier layer 42 constituting the barrier film A according to the present invention described above First, a coating film 51 made of a polyurethane resin composition or a polyester resin composition containing at least a silane coupling agent and a filler is provided on the surface of the physical layer 42c. A laminate material B according to the present invention can be manufactured by providing a heat-seal resin layer 53 on the adhesive layer 52.

  In FIG. 4, the reference numeral 41 represents the same meaning as the reference numeral 41 shown in FIG. 3, that is, a base film made of a polyamide resin film, and reference numerals 42a and 42b. Represents the same meaning as the reference numerals 42a and 42b shown in FIG.

  In the laminated material according to the present invention, although not shown, a desired exterior material can be optionally provided on the outer layer surface of the base film made of the polyamide-based resin film. A desired printed pattern layer can be provided on the film surface of the film, and a desired intermediate substrate is optionally provided between the coating film and the heat seal resin layer. It is something that can be done.

  Thus, in the present invention, other base materials are arbitrarily laminated depending on the purpose of use, usage form, application, etc., and the laminate material according to the present invention having various forms is designed and manufactured. It is something that can be done.

  Next, in the present invention, an example of the liquid-filled packaging pouch according to the present invention will be described. As such a liquid-filled packaging pouch, as shown in FIG. First, two laminated materials B and B are prepared using the material B, and the surfaces of the heat-seal resin layer 53 located on the innermost layer are opposed to each other, and thereafter, the periphery of the outer periphery. The present invention comprises a three-sided seal type flexible packaging bag by forming a seal part 61, 61, 61 and providing an opening 62 in the upper part by heat-sealing three sides of the end of the bag. Such a liquid-fill packaging sachet C can be manufactured.

  Next, in the present invention, as shown in FIG. 6, from the opening 62 of the liquid-filled packaging pouch C according to the present invention, which is made of the three-side seal type soft packaging bag manufactured as described above, for example, dressing , Hot-fill packaging of liquid contents 63 composed of liquid seasonings such as soy sauce, sauce, mayonnaise, miso, vinegar, etc., then heat seal the upper opening 62 and A package product D using the liquid-filled packaging sachet C according to the present invention having various forms, for example, by performing boil processing, retort processing, etc. Can be manufactured.

  In the present invention, the liquid-filled sachet according to the present invention is limited to the liquid-filled sachet according to the present invention which is composed of the illustrated three-way seal type soft wrapping bag shown above. Needless to say, depending on the purpose, application, etc., flexible packaging of any shape such as two-sided seal type, four-sided seal type, gusset type, self-standing type, pillow type, etc. It goes without saying that liquid-filled packaging sachets made of sachets can be produced.

  The manufacturing method of the laminated material according to the present invention will be described more specifically. Although not shown, for example, on the surface of the silicon oxide layer forming the barrier layer constituting the barrier film according to the present invention described above. First, a coating film made of a polyurethane-based resin composition or a polyester-based resin composition containing at least a silane coupling agent and a filler is provided, and an adhesive for laminating is further formed on the coating film. Forming an agent layer, and then laminating a desired substrate such as a plastic film using the dry lamination method through the coating film and the laminating adhesive layer, etc. Laminates according to the present invention having various forms can be produced.

  Alternatively, in the present invention, although not shown in the drawings, for example, first on the surface of the silicon oxide layer forming the barrier layer constituting the barrier film according to the present invention, first, at least a silane coupling agent and a filler. A coating film made of a polyurethane-based resin composition or a polyester-based resin composition, and an anchor coating agent layer or the like is further formed on the coating film. Extrusion lamination method in which various resins are melt-extruded through a coating film and an anchor coating agent layer, and a desired base material such as a plastic film is laminated through the melt-extruded resin layer By laminating using the above, the laminated material according to the present invention having various forms can be produced.

  In addition, in this invention, another base material can also be arbitrarily laminated | stacked using the above lamination methods, Thereby, the laminated material concerning this invention which consists of various forms can be manufactured. In the present invention, other base materials are arbitrarily laminated depending on the purpose of use, use form, application, etc., and the laminate material according to the present invention having various forms is designed and manufactured. It is something that can be done.

  Next, in the present invention, the coating film constituting the laminated material will be described. As such a coating film, first, a polyurethane resin or a polyester resin is used as a main component of the vehicle, and the polyurethane film 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. Thus, a coating film can be formed.

In the present invention, the thickness of the coating film is preferably about 0.1 g / m ^{2 to} 5.0 g / m ² (dry state), for example.

  Accordingly, in the present invention, the above-described coating film is used to form a barrier layer constituting the barrier film according to the present invention, an adhesive layer, and a heat seal. In addition to improving close adhesion with the adhesive resin layer, etc., and improving the elongation of the coating film, for example, improving post-processing suitability such as laminating or bag making, The occurrence of cracks and the like in the silicon oxide layer constituting the barrier film according to the present invention is prevented.

  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, the adhesive layer, the heat-sealable resin layer, and the like is improved and the coating is improved. -To improve the elongation of the coating film, for example, improve the suitability for post-processing such as laminating or bag making, and prevent the occurrence of cracks in the silicon oxide layer 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 coating film 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 and increases its 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 polyacrylic acid ester 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 adhesive, polyurethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate 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 bonding 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 via an anchor coating agent layer such as the above-described anchor coating agent.

  Next, in the present invention, the heat-seal resin constituting the sheet-seal resin layer forming the innermost layer or the like of the laminated material according to the present invention is, for example, melted by heat and melted mutually. Various resins having heat-seal properties that can be worn can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear (linear) low-density polyethylene. , Ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer- Polyolefin resins such as polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resin, poly One or more kinds of resins such as (meth) acrylic resins, polyvinyl chloride resins, and the like can be used.

  Accordingly, in the present invention, the acrylic resin layer may be a film or sheet of the resin as described above, or a coating film state of a composition containing the resin, or the like. Can be used.

  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 an exterior material laminated on the outer layer surface of the laminated material according to the present invention, or as an intermediate base material laminated between the coating film and the heat sealable resin layer, For example, as a basic material of a laminated material, a resin film having excellent properties in mechanical, physical, chemical, etc., particularly having strength and toughness and heat resistance Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal system, and the like can be used. A tough resin film or sheet such as resin, fluorine-based resin, or the like 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, for example, various paper base materials constituting the paper layer can be used as the exterior material, intermediate base material, etc. constituting the above laminated material. In the present invention, the paper base material has formability, bending resistance, rigidity, etc., for example, a paper base material having a strong sizing property or unbleached paper, or pure white roll paper, kraft paper Paper base materials such as paperboard and processed paper, and the like 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-described lamination, if necessary, the surface of each material constituting each lamination surface is subjected to, for example, corona discharge treatment, ozone treatment, plasma treatment, flame treatment, and the like. In addition, for example, an anchor coating agent such as isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, polyurethane, polyacrylic, etc. Anchor coating agents such as laminating adhesives such as those based on polyester, polyester, epoxy, polyvinyl acetate, cellulose, etc., 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 according to the present invention.
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, as the coating film provided on the surface of the silicon oxide layer such as silicon oxide or aluminum oxide, in addition to the primer layer made of the polyurethane-based or polyester-based resin composition, Further, 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, A primer agent layer can be formed using a resin composition having a vehicle-based resin or the like as a main component of a 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 producing a liquid-filled packaging sachet according to the present invention using the laminated material according to the present invention. For example, for liquid-filled packaging according to the present invention When the sachet is a soft packaging bag made of a plastic film or the like, use the laminated material according to the present invention produced by the method as described above, with the surface of the heat-sealable resin layer of the inner surface layer facing, The bag body can be formed by folding the two sheets or overlapping the two sheets, and then heat sealing the peripheral edge of the outer periphery to provide a seal portion.
Thus, as the bag-making method, the laminated material according to the present invention is folded with the inner surface layers facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, Side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, jointed seal type (pillary seal type), with pleats Pouches for liquid-filled packaging comprising various forms according to the present invention, which are heat-sealed in the form of a heat seal such as a seal type, flat bottom seal type, square bottom seal type, etc. Can be manufactured.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. In the present invention, a tube container or the like can also be manufactured using the laminated material according to the present invention. .
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, for example, a one-piece type, two-piece type, or other spout, or an opening / closing zipper can be arbitrarily attached to the liquid-filled packaging pouch as described above. .

Next, as a liquid-filled packaging sachet according to the present invention, in the case of a liquid-filled sachet containing a paper base material, for example, as a laminated material according to the present invention, a laminated material in which a paper base material is laminated is manufactured, and from this A blank plate for manufacturing a desired liquid-filled packaging sachet is manufactured, and then the body, the bottom, the head, etc. are manufactured using the blank plate, for example, a brick type, a flat type or a gate type. A bell top type liquid-filled packaging sachet 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 liquid-filled packaging sachet according to the present invention manufactured as described above includes various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and the like. It is used for filling and packaging of articles.
Thus, in the present invention, in particular, for example, a sachet for liquid filling and packaging, such as dressing, soy sauce, sauce, mayonnaise, miso, vinegar, etc. Useful as packaging containers for filling and packaging foods and beverages, such as sachets for filling and packaging round buns, soft packaging bags for filling and packaging fresh confectionery, etc., or soft packaging bags for filling and packaging boiled or retort foods, etc. It is a thing.

Hereinafter, the present invention will be described in more detail with reference to examples.
First, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared as a substrate 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 65 mm and the second layer has a thickness of 60 mm on one corona-treated surface of a biaxially stretched nylon 6 film having a thickness of 15 μm. A two-layered silicon oxide layer having a thickness of 125 mm was formed into a barrier film according to the present invention.
Next, a glow discharge plasma generator is used on the surface of the silicon oxide layer of the barrier film produced above, and the power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: Using a mixed gas of 2.5 (unit: slm), performing oxygen / argon mixed gas plasma processing at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min, the film surface of the silicon oxide layer A plasma-treated surface having a surface tension of 54 dyne / cm or more was formed.
Next, 1.0% by weight of silane coupling agent, 1.0% by weight of silica powder, 13-15% by weight of polyurethane resin, 3-4% by weight of nitrocellulose are formed on the surface of the plasma-treated surface formed as described above. A polyurethane resin composition comprising 31 to 38% by weight of toluene, 29 to 30% by weight of methyl ethyl ketone (MEK), and 15 to 16% by weight of isopropyl alcohol (IPA) was prepared. Coating is carried out using a method, followed by heat drying to form a coating thin film (dry film thickness, 4.0 g / m ² ) from the above polyurethane resin composition. A nylon film was produced.
Further, a two-component curable polyurethane adhesive was coated on the surface of the coating thin film of the barrier nylon film produced as described above using the roll coating method in the same manner as described above. Subsequently, it was heat-dried to form an adhesive layer (dry film thickness, 1.0 g / m ² ).
Thereafter, low-density polyethylene was used on the surface of the adhesive layer formed above, and this was melt-extruded to a thickness of 60 μm to produce a laminate according to the present invention.
Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

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.
Next, a plasma-treated surface is formed on the surface of the silicon oxide layer of the barrier film produced as described above in the same manner as in Example 1, and then a silane coupling agent is formed on the surface of the plasma-treated surface. 1.0 wt%, silica powder 1.0 wt%, polyurethane resin 13-15 wt%, nitrocellulose 3-4 wt%, toluene 31-38 wt%, methyl ethyl ketone (MEK) 29-30 wt%, A polyurethane-based resin composition comprising 15 to 16% by weight of isopropyl alcohol (IPA) was prepared, and this was coated using a roll coating method, followed by heat drying, A coating thin film (dry film thickness, 4.0 g / m ² ) was formed from the polyurethane resin composition to produce a barrier nylon film according to the present invention.
Further, a two-component curable polyurethane adhesive was coated on the surface of the coating thin film of the barrier nylon film produced as described above using the roll coating method in the same manner as described above. Subsequently, it was heat-dried to form an adhesive layer for laminating (dry film thickness, 4.0 g / m ² ).
Thereafter, a low-density polyethylene film having a thickness of 60 μm was dry-laminated on the surface of the laminating adhesive layer formed as described above to produce a laminated material according to the present invention.
Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

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, As in Example 2, a laminated material and a liquid-filled packaging pouch according to the present invention were produced.

  In Example 2 above, tetramethoxysilane (hereinafter referred to as TMOS) is used instead of HMDSO, which is an organosilicon compound constituting the raw material gas, and the others are exactly the same as in Example 2 above. In the same manner as in Example 2, the laminated material and the liquid-filled packaging pouch according to the present invention were manufactured.

  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. Similarly to Example 2 above, a laminated material and a liquid-filled packaging pouch according to the present invention were 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 laminated material and a liquid-filled packaging pouch according to the present invention were produced in the same manner as in Example 2 above.

  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. Similarly to the above, a laminated material and a liquid-filled packaging pouch according to the present invention were produced.

First, as a substrate film, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared, and a plasma chemical vapor phase in which two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. 2 were installed. Attached to the growth apparatus.
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 65 mm of the first layer, a thickness of 60 mm of the second layer, and a total thickness of 125 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 │ └───┴───────────────────────────┘

Next, a glow discharge plasma generator is used on the surface of the silicon oxide layer of the barrier film produced above, and the power is 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: Using a mixed gas of 2.5 (unit: slm), performing oxygen / argon mixed gas plasma processing at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min, the film surface of the silicon oxide layer A plasma-treated surface having a surface tension of 54 dyne / cm or more was formed.
Next, 1.0% by weight of silane coupling agent, 1.0% by weight of silica powder, 13 to 15% by weight of polyester resin, and 3 to 4% by weight of nitrocellulose are formed on the surface of the plasma-treated surface formed above. A polyester resin composition comprising 31 to 38% by weight of toluene, 29 to 30% by weight of methyl ethyl ketone (MEK), and 15 to 16% by weight of isopropyl alcohol (IPA) was prepared. Coating is performed using a method, followed by heat drying to form a coating thin film (dry film thickness, 4.0 g / m ² ) using the above-described polyester resin composition. A nylon film was produced.
Furthermore, on the surface of the coating thin film of the barrier nylon film produced above, a gravure printing ink composition was used, and a desired printed pattern layer consisting of letters, figures, symbols, and patterns was printed by a gravure printing method. Thereafter, a two-component curable polyurethane adhesive is coated on the entire surface including the printed pattern layer in the same manner as described above using a roll coating method, and then thermally dried to adhere. An agent layer (dry film thickness, 1.0 g / m ² ) was formed.
Thereafter, low-density polyethylene was used on the surface of the adhesive layer formed above, and this was melt-extruded to a thickness of 60 μm to produce a laminate according to the present invention.
Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

First, as a substrate film, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared, and a plasma chemical vapor phase in which two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. 2 were installed. Attached to the growth apparatus.
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 40 mm, a third layer thickness of 45 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 │ └───┴───────────┴─ ──────────────┘

Next, a plasma-treated surface is formed on the surface of the silicon oxide layer of the barrier film produced as described above in the same manner as in Example 8, and then a silane coupling agent is formed on the surface of the plasma-treated surface. 1.0 wt%, silica powder 1.0 wt%, polyurethane resin 13-15 wt%, nitrocellulose 3-4 wt%, toluene 31-38 wt%, methyl ethyl ketone (MEK) 29-30 wt%, A polyurethane-based resin composition comprising 15 to 16% by weight of isopropyl alcohol (IPA) was prepared, and this was coated using a roll coating method, followed by heat drying, A coating thin film (dry film thickness, 4.0 g / m ² ) was formed from the polyurethane resin composition to produce a barrier nylon film according to the present invention.
Further, a two-component curable polyurethane adhesive was coated on the surface of the coating thin film of the barrier nylon film produced as described above using the roll coating method in the same manner as described above. Subsequently, it was heat-dried to form an adhesive layer for laminating (dry film thickness, 4.0 g / m ² ).
Thereafter, a low-density polyethylene film having a thickness of 60 μm was dry-laminated on the surface of the laminating adhesive layer formed as described above to produce a laminated material according to the present invention.
Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

First, as a substrate film, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared, and a plasma chemical vapor phase in which two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. 2 were installed. Attached to the growth apparatus.
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 having a first layer thickness of 45 mm, a second layer thickness of 40 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 │ └───┴───────── ──┴───────────────┘

Next, a plasma-treated surface is formed on the surface of the silicon oxide layer of the barrier film produced as described above in the same manner as in Example 8, and then a silane coupling agent is formed on the surface of the plasma-treated surface. 1.0 wt%, silica powder 1.0 wt%, polyurethane resin 13-15 wt%, nitrocellulose 3-4 wt%, toluene 31-38 wt%, methyl ethyl ketone (MEK) 29-30 wt%, A polyurethane-based resin composition comprising 15 to 16% by weight of isopropyl alcohol (IPA) was prepared, and this was coated using a roll coating method, followed by heat drying, A coating thin film (dry film thickness, 4.0 g / m ² ) was formed from the polyurethane resin composition to produce a barrier nylon film according to the present invention.
Further, a two-component curable polyurethane adhesive was coated on the surface of the coating thin film of the barrier nylon film produced as described above using the roll coating method in the same manner as described above. Subsequently, it was heat-dried to form an adhesive layer for laminating (dry film thickness, 4.0 g / m ² ).
Thereafter, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is dry-laminated on the surface of the laminating adhesive layer formed as described above, and then the biaxially stretched polyethylene terephthalate film is further laminated. In the same manner as described above, the surface was coated using a roll coating method, and then heat-dried to form a laminating adhesive layer (dry film thickness: 4.0 g / m ² ). After the formation, the laminated material according to the present invention was manufactured by dry laminating a low-density polyethylene film having a thickness of 60 μm on the surface of the laminating adhesive layer formed above. Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

First, as a substrate film, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared, and a plasma chemical vapor phase in which two supply pipes capable of independently controlling the flow rate introduced into each chamber as shown in FIG. 2 were installed. Attached to the growth apparatus.
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 40 mm, a second layer thickness of 45 mm, a first layer thickness of 45 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 │ └───┴────────── ─┴───────────────┘

Next, a plasma-treated surface is formed on the surface of the silicon oxide layer of the barrier film produced as described above in the same manner as in Example 8, and then a silane coupling agent is formed on the surface of the plasma-treated surface. 1.0 wt%, silica powder 1.0 wt%, polyester resin 13-15 wt%, nitrocellulose 3-4 wt%, toluene 31-38 wt%, methyl ethyl ketone (MEK) 29-30 wt%, A polyurethane-based resin composition comprising 15 to 16% by weight of isopropyl alcohol (IPA) was prepared, and this was coated using a roll coating method, followed by heat drying, A coating thin film (dry film thickness, 4.0 g / m ² ) was formed from the polyurethane resin composition to produce a barrier nylon film according to the present invention.
Further, a two-component curable polyurethane adhesive is coated on the surface of the biaxially stretched nylon 6 film of the barrier nylon film produced as described above using a roll coating method. Then, it is thermally dried to form an adhesive layer (dry film thickness, 4.0 g / m ² ), and then a biaxially stretched polypropylene film having a thickness of 20 μm is formed on the surface of the adhesive layer formed above. On the other hand, a two-component curable polyurethane adhesive is applied to the surface of the coating thin film of the barrier nylon film produced above using the roll coating method as described above. It was coated and then heat-dried to form an adhesive layer (dry film thickness, 1.0 g / m ² ).
Thereafter, low-density polyethylene was used on the surface of the adhesive layer formed above, and this was melt-extruded to a thickness of 60 μm to produce a laminate according to the present invention.
Next, using the above laminated material, mounting it on a bag making machine to make a bag, manufacturing a three-sided seal type plastic sachet, then filling the plastic sachet with dressing Then, after that, the opening was heat sealed and a packaged product filled with the contents and packaged was manufactured. The above packaged product has excellent barrier properties, no odor leakage, excellent fragrance retention, long-term storage and storage properties, and excellent distribution suitability. It was.

  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, as in Example 2 above, a laminated material and a liquid-filled packaging pouch according to the present invention were produced.

  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. In the same manner as in Example 9, a laminated material and a liquid-filled packaging pouch according to the present invention were produced in the same manner as in Example 9.

(Comparative Example 1)
First, a biaxially stretched nylon 6 film having a thickness of 15 μm was prepared as a substrate 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.
Hereinafter, using the barrier film produced above, a laminated material and a liquid-filled packaging pouch were produced in the same manner as in Example 1 above, in the same manner as in Example 1 above.

(Comparative Example 2)
In the above Comparative Example 1, except that the coating thin film made of the polyurethane resin composition was not formed, exactly the same as in the above Comparative Example 1, the same as in the above Example 1, a laminated material, A liquid-filled sachet was produced.

(Comparative Example 3)
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 exactly the same manner as in Example 1, a laminated material and a liquid-filled packaging pouch were produced in the same manner as in Comparative Example 1 above.

(Comparative Example 4)
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 exactly the same manner as in Example 1, a laminated material and a liquid-filled packaging pouch were produced in the same manner as in Comparative Example 1 above.

(Comparative Example 5)
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) Otherwise, the laminated material and the liquid-filled packaging sachet were manufactured in the same manner as in Example 1 above, exactly as in Example 1 above.

(Comparative Example 6)
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, Similar to Example 2, laminate, to produce a liquid-filled packaging pouch.

(Comparative Example 7)
In Comparative Example 1 described above, instead of using a biaxially stretched nylon 6 film having a thickness of 15 μm as a base film, a thermosetting acrylic resin is formed on one surface of the base film as a main component of the vehicle. 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. In the same manner as in Comparative Example 1, a laminated material and a liquid-filled packaging pouch were produced in the same manner as in Comparative Example 1 above.

(Experimental example 1)
Oxygen permeability and water vapor permeability were measured for the laminated materials and liquid-filled packaging pouches produced in Examples 1 to 13 and Comparative Examples 1 to 7.
(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)
┌─────┬────────────┬────────────┐ │ │ Laminate │ Pouch for liquid filling │ │ ├──── ─┬──────┼─────┬──────┤ │ │ Oxygen permeability │ Water vapor permeability │ Oxygen permeability │ Water vapor permeability │ ├─────┼─── ──┼──────┼─────┼──────┤ │Example 1 │ 1.8 │ 6.7 │ 1.6 │ 2.3 │ ├ ────── ┼─────┼──────┼─────┼──────┤ │Example 2 │ 1.3 │ 4.9 │ 1.3 │ 1.5 │ ├─ ────┼─────┼──────┼─────┼──────┤ │Example 3 │ 1.1 │ 5.4 │ 0.9 │ １． 9 │ ├─────┼─────┼──────┼─────┼──────┤ │Example 4 │ 0.9 │ 7.5 0.8 │ 2.1 │ ├─────┼─────┼──────┼─────┼──────┤ │Example 5 │ 1.3 │ 6.8 │ 1.3 │ 2.3 │ ├─────┼─────┼─────┼─────┼──────┤ │Example 6 │ 0.6 │ 5.5 │ 0.5 │ 1.6 │ ├─────┼─────┼──────┼─────┼──────┤ │ │ Example 7 │ 0.7 │ 5.2 │ 0.6 │ 1.5 │ ├─────┼─────┼──────┼─────┼───── ──┤ │Example 8 │ 0.8 │ 5.8 │ 0.7 │ 1.7 │ ├─────┼─────┼──────┼─────┼ ──────┤ │Example 9 │ 0.9 │ 6.1 │ 0.8 │ 1.9 │ ├─────┼─────┼──────┼── ───┼──── ──┤ │Example 10│ 0.7 │ 5.4 │ 0.6 │ 1.8 │ ├ ─────┼─────┼──────┼─────┼ ──────┤ │Example 11│ 0.5 │ 4.8 │ 0.5 │ 1.5 │ ├─────┼─────┼──────┼── ───┼──────┤ │Example 12│ 1.5 │ 4.5 │ 1.4 │ 1.2 │ ├─────┼─────┼───── ─┼─────┼──────┤ │Example 13│ 0.8 │ 5.7 │ 0.8 │ 1.7 │ ├─────┼─────┼─ ─────┼─────┼──────┤ │Comparative Example 1 │ 3.2 │ 13.1 │ 3.0 │ 5.6 │ ├─────┼─── ──┼──────┼─────┼──────┤ │Comparative Example 2 │ 3.3 │ 13.1 │ 3.2 │ 5.7 │ ├ ───── ─────┼──────┼─────┼──────┤ │Comparative Example 3 │ 2.7 │ 18.9 │ 2.5 │ 7.9 │ ├── ───┼─────┼──────┼─────┼──────┤ │Comparative Example 4 │ 3.0 │ 15.2 │ 3.0 │ 7.5 │ ├─────┼─────┼──────┼─────┼──────┤ │Comparative Example 5 │ 2.0 │ 8.4 │ 1.6 │ 2.5 │ ├─────┼─────┼──────┼─────┼──────┤ │Comparative Example 6 │ 1.9 │ 8.2 │ 1.2 │ 2.2 │ ├─────┼─────┼──────┼─────┼──────┤ │Comparative Example 7 │ 3.3 │ 12.5 │ 3.2 │ 5.4 │ └─────┴─────┴──────┴─────┴──────┘ Table 5 above In Units of oxygen permeability are ^{[cc / m 2 / day · 23} ℃ · 90% RH ], the unit of water vapor transmission rate is ^{[g / m 2 / day · 40} ℃ · 90% RH ].

  As is clear from the results shown in Table 5 above, the laminated material and the liquid-filled packaging pouch according to the present invention were excellent in oxygen permeability and water vapor permeability.

(Experimental example 2)
About the packaging product manufactured in said Examples 1-13 and Comparative Examples 1-7, this was put into the glass bottle, the lid | cover, and it preserve | saved at 40 degreeC oven for 4 days.
Thereafter, the lid was opened, and whether or not there was a smell was examined with human senses, and the perfume 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 6 below.

(Table 6)
┌ ─────┬───────┐ │ │ 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 │ △ │ ├─────┼─ ──────┤ │Comparative Example 7 │ △ │ └─────┴───────┘

  As is clear from the results shown in Table 6 above, the laminated material according to the present invention using the barrier film according to the present invention was excellent in perfume retention.

(Experimental example 3)
The laminate strength was measured for the laminated materials produced in Examples 1 to 13 and Comparative Examples 1 to 7, and the liquid-filled packaging pouches produced using the laminated materials.
This uses a laminating strength tester [Oleentech Co., Ltd., model name, Tensilon universal tester], under the conditions of 15 mm width x 90 ° peel angle, 5 kg load cell, 50 mm / min peel rate. went.
In the tearability test, a 5 mm incision was made at the end of the laminated material, and teared by hand, and the tearing feeling was evaluated.
When it was difficult to tear, it was marked with ◯, when it was torn somewhat, it was marked with Δ, and when it was torn, it was marked with ×.
The results are shown in Table 7 below.

(Table 7)
┌─────┬───────┬──────────┬─────┐ │ │ Laminated material │ Liquid filling packaging │ Tearability │ │ │ Laminate Strength │ small bag laminating strength │ ├ ├─────┼───────┼──────────┼─────┤ │Example 1 │ Unpeelable │ No peeling │ ○ │ ├─────┼───────┼──────────┼─────┤ │Example 2 │ No peeling │ No peeling │ ○ │ ├─────┼───────┼──────────┼─────┤ │Example 3 │ No peeling │ No peeling │ ○ │ ├─── ──┼───────┼──────────┼─────┤ │Example 4 │ No peeling │ No peeling │ ○ │ ├ ──────┼── ─────┼──────────┼─────┤ │Example 5 │ Unpeelable │ No peeling │ ○ │ ├─────┼───────┼──────────┼─────┤ │Example 6 │ No peeling │ No peeling │ ○ │ ├─────┼───────┼──────────┼─────┤ │Example 7 │ No peeling │ No peeling │ ○ │ ├─── ──┼───────┼──────────┼─────┤ │Example 8 │ No peeling │ No peeling │ ○ │ ├ ──────┼── ─────┼──────────┼─────┤ │Example 9 │ No peeling │ No peeling │ ○ │ ├ ─────┼─────── ┼──────────┼─────┤ │Example 10│ No peeling │ No peeling │ ○ │ ├─────┼───────┼──── ──────┼─────┤ │Example 11│ Unpeelable │ Unpeelable │ ○ │ ──── ──┼───────┼──────────┼─────┤ │Example 12│ No peeling │ No peeling │ ○ │ ├─────┼── ─────┼──────────┼─────┤ │Example 13│ No peeling │ No peeling │ ○ │ ├ ──────┼─────── ┼──────────┼─────┤ │Comparative example 1 │ No peeling │ No peeling │ ○ │ ├─────┼───────┼──── ──────┼─────┤ │Comparative Example 2 │ 320 │ 315 │ × │ ├─────┼───────┼──────────┼ ─────┤ │Comparative example 3 │ No peeling │ No peeling │ ○ │ ├────┼───────┼──────────┼───── ┤ │Comparative example 4 │ No peeling │ No peeling │ ○ │ ├─────┼───────┼────── ────┼─────┤ │Comparative example 5 │ No peeling │ No peeling │ ○ │ ├─────┼───────┼──────────┼ ─────┤ │Comparative Example 6 │ No peeling │ No peeling │ ○ │ ├────┼───────┼──────────┼────── │ │Comparative example 7 │ No peeling │ No peeling │ ○ │ └─────┴───────┴──────────┴─────┘ Table 7 above The unit of laminating strength is [gf / 15 mm].

  As is clear from the results shown in Table 7 above, the laminated material and the liquid-filled packaging pouch according to the present invention using the barrier film according to the present invention are excellent in laminating strength and also in tearability. It was excellent.

(Experimental example 4)
In the barrier film produced in Example 2 and Comparative Example 1 above, after forming a silicon oxide layer on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, the silicon oxide The change of the component in the depth direction of the layer was measured.
This is because a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm on which a silicon oxide layer is formed is measured from the film surface of the silicon oxide layer using an X-ray photoelectron spectroscopy (XPS). Elemental analysis was performed in the direction, and the silicon, oxygen, and carbon contents detected at that time were measured and evaluated.
The results are shown in Table 8 below.
Further, in the barrier film produced in Example 2 and Comparative Example 1, a silicon oxide layer was formed on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, and then the silicon oxide Measurement of IR absorption peak position based on Si—O—Si stretching vibration and IR absorption peak strength based on Si—CH ₃ stretching vibration of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm. did.
This is a 12-μm thick biaxially stretched polyethylene terephthalate film on which a silicon oxide layer is formed, equipped with a multiple reflection measuring device (manufactured by JASCO Corporation, model name, ATR-300 / H). It measured with the conversion type | mold infrared spectrophotometer (The JASCO Corporation make, model name, Herschel FT / IR-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 8 below.

(Table 8)
┌───────┬──────────┬─────────┬──────┐ │ │ Si: O: C │Si-O-Si Pi-│Si-CH ₃ │ │ │ │ Position (cm ^-1 ) │ Absorption Strength│ ├─┬─────┼──────────┼───────── ─┼──────┤ │ │1 layer │ │ │ │ │ Real │ (Surface) │100: 160: 90│ 1038 │0.028 │ │ ├ ──────┼──── ──────┼─────────┼──────┤ │Example│Layer 2 │100: 185: 13│ 1065 │0.010 │ │2├──── ─┼──────────┼─────────┼──────┤ │ │3 layers │ │ │ │ │ │ (base material side) │100: 170 : 85│ 1040 │0.027 │ ├─┬─────┼──────────┼─ ───────┼──────┤ │ │1 layer │ │ │ │ │ ratio│ (surface) │100: 180: 17│ 1060 │0.012 │ │comparison──── ─┼──────────┼─────────┼──────┤ │Example│2 layers │100: 185: 15│ 1065 │0.011 │ │ 1├─────┼──────────┼─────────┼──────┤ │ │3 layers │ │ │ │ │ │ (base material Side) │100: 188: 15│1065 │0.012 │ └─┴─────┴──────────┴─────────┴────── ─┘

From the results shown in Table 8 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.

  In the present invention, a polyamide-based resin film is used as a base film, and the silicon oxide layer constituting the barrier layer has excellent adhesion to the polyamide-based resin film, and its extensibility, flexibility, flexibility In addition, the silicon oxide layer is excellent in gas barrier properties that prevent the passage of oxygen gas, water vapor, and the like without introducing foreign matter, dust, or the like that causes cracks into the silicon oxide layer. The present invention relates to a laminated material using a very useful barrier film in which no deterioration in performance is observed as a barrier material and a liquid-filled packaging sachet using the same.

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. 4 is a schematic cross-sectional view showing an example of the layer structure of the laminated material according to the present invention manufactured using the barrier film shown in FIG. FIG. 5 is a schematic perspective view showing an example of the liquid-filled packaging pouch according to the present invention, which is made using the laminated material shown in FIG. FIG. 6 is a schematic perspective view showing an example of the packaged product according to the present invention, which is manufactured by using the liquid-filled packaging pouch shown in FIG. 5 and filling and packaging the contents therein.

Explanation of symbols

A Barrier film B Laminated material C Liquid-filled packaging sachet D Packaging product 41 Base film made of polyamide resin film 42 Barrier layer 42a Silicon oxide layer 42b Silicon oxide layer 42c Silicon oxide layer 51 Coating film 52 Adhesive Layer 53 Heat Seal Resin Layer 61 Seal Part 62 Opening 63 Liquid Content 64 Upper Seal Layer

Claims (18)

It consists of a polyamide resin film and a barrier layer provided on one surface of the polyamide resin film, and the barrier layer uses at least two film forming chambers, and each chamber In addition, it was 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. Two or more film-forming mixed gas compositions are used, each of the film-forming mixed gas compositions is used to form two or more layers of silicon oxide layers formed by plasma enhanced chemical vapor deposition, Each of the silicon oxide layers contains carbon atoms in the film, and on the barrier layer of the barrier film formed by different content of the carbon atoms for each silicon oxide layer, At least a silane coupling agent and a filler A coating film made of a polyurethane-based resin composition or a polyester-based resin composition is provided, and a heat-seal resin layer is further provided on the coating film via an adhesive layer. A laminated material characterized by The loading material according to claim 1, wherein the polyamide-based resin film is provided with an exterior material on an outer layer surface thereof. The laminated material according to any one of claims 1 and 2, wherein the coating film is provided with a printed pattern layer on the film surface. The laminated material according to any one of claims 1 to 3, wherein the coating film and the heat sealable resin layer are provided with an intermediate base material between the layers. The laminated material according to any one of claims 1 to 4, 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 laminated material as described in any one of Claims 1-5. The laminate material according to any one of claims 1 to 6, wherein the inert gas is composed of 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). The laminate material according to any one of claims 1 to 7, wherein the laminate material has a composition ratio. 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). The laminate material according to any one of claims 1 to 8, wherein the laminate material has a composition ratio. 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. The laminate according to claim 8, wherein the laminate material 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 laminated material according to claim 9, wherein the laminated material 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 laminated material according to any one of claims 1 to 11, comprising a silicon oxide layer formed by preparing a film of 20 to 200 mm and a third layer of 20 to 200 mm. The silicon oxide layer contains carbon atoms in the film, and the carbon content in the film increases in the depth direction from the film surface. 13. The laminated material according to any one of 12 above. The laminated material according to any one of claims 1 to 13, wherein the plasma chemical vapor deposition method comprises a low temperature plasma chemical vapor deposition method. It consists of a polyamide resin film and a barrier layer provided on one surface of the polyamide resin film, and the barrier layer uses at least two film forming chambers, and each chamber In addition, it was 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. Two or more film-forming mixed gas compositions are used, each of the film-forming mixed gas compositions is used to form two or more layers of silicon oxide layers formed by plasma enhanced chemical vapor deposition, Each of the silicon oxide layers contains carbon atoms in the film, and on the barrier layer of the barrier film formed by different content of the carbon atoms for each silicon oxide layer, At least a silane coupling agent and a filler A coating film made of a polyurethane-based resin composition or a polyester-based resin composition is provided, and a heat-sealable resin layer is further provided on the coating film via an adhesive layer Using a laminated material made of the above, and making the heat-sealable resin layer face to face each other, and then heat-sealing the outer peripheral edge to provide a seal. A pouch for liquid-filled packaging. 16. The liquid-filled packaging pouch according to claim 15, wherein the polyamide-based resin film is provided with an exterior material on the outer layer surface. 17. The liquid-filled packaging pouch according to claim 15, wherein the coating film is provided with a printed pattern layer on the film surface. 18. A sachet for liquid-filled packaging according to any one of claims 15 to 17, wherein the coating film and the heat-seal resin coating are provided with an intermediate substrate between the layers. .

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