JP5157149B2 - Method and apparatus for producing gas barrier film - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film obtained by coating a gas barrier composition with a gravure roll on an inorganic oxide vapor-deposited film formed on a base film, and more specifically, both ends of a gravure roll. The present invention relates to providing the plate depth of the engraving near the center shallower than the plate depth of the engraving near the center of the gravure roll.

Conventionally, as packaging materials for filling and packaging foods, drinks, chemicals, miscellaneous goods, etc., various kinds of materials that block or block the transmission of oxygen gas, water vapor, etc. in order to prevent the contents from being altered, discolored, etc. A barrier laminate having the following form has been developed and proposed. As an application of such a barrier laminate, for example, there is a retort pouch, which is generally subjected to a sterilization process of about 20 to 60 minutes at a temperature of about 110 to 130 ° C. and a pressure of 1 to 3 kgf / cm ² · G. As a barrier laminate material used under such retort conditions, for example, on a film of aluminum oxide or silicon oxide formed on a base film such as a biaxially stretched polyester film or nylon film, at least one more Alkoxide and a poly (vinyl alcohol) resin and / or an ethylene / vinyl alcohol copolymer, and polycondensed by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. There is a gas barrier film (Patent Document 1) obtained by coating a coating film made of a gas barrier composition with a gravure roll, which is widely used as having high gas barrier properties without being affected by temperature and humidity. Also, for example, in the production process of a thermal stencil master having a porous layer on one surface of a thermoplastic resin film having a thickness of 0.5 to 5 μm, application of a coating solution for forming the porous layer Sometimes this gravure roll coat etc. is used for this heat-sensitive stencil printing so that the amount of the coating liquid adhering to the boundary between the coating liquid and the thermoplastic resin film decreases sequentially and becomes substantially zero at the edge. There is also one that can prevent the generation of wrinkles that occur when a master is manufactured (Patent Document 2).
JP 2006-116704 A JP-A-10-217629

  However, when producing a laminated film, particularly a gas barrier film, using a conventional gravure roll as in Patent Document 1, the width of the substrate film having the deposited film is on the deposited film of the substrate film. The coating width of the gas barrier composition to be coated becomes narrower, and at that time, the shrinkage stress of the gas barrier composition concentrates on the base film having the vapor deposition film at the end of the gas barrier composition, This gas barrier is formed so that the end portion of the base film having a non-coated vapor-deposited film is easily broken toward the coated surface side of the gas barrier composition, and further, the coated end portion of the gas barrier composition is raised. Since the coating amount of the functional composition is increased and the end portion of the base film having such an uncoated vapor deposition film is more likely to be broken, the gas barrier composition is applied in the production process. The problem that the gas barrier film cannot be uniformly wound around the drum and an extra step for cutting the bent portion of the end portion must be provided, and the productivity is lowered due to such a defect in the manufacturing process. There was a problem. Moreover, in the gravure roll coat used when manufacturing the thermosensitive stencil printing master described in Patent Document 2, although there is a description of gradually decreasing the depth of grooves at both ends of the engraving portion in this gravure roll coat, the gravure roll coat gradually becomes shallower. The depth is not a quantitative disclosure, so the content is unknown, and the target product is a heat-sensitive stencil master, on an inorganic oxide vapor-deposited film formed on a substrate film Moreover, it is different from a gas barrier film formed by coating a gas barrier composition with a gravure roll.

  Accordingly, an object of the present invention is to provide a gas barrier film manufacturing method and a manufacturing apparatus that prevent bending of the gas barrier film substrate end portion and improve productivity.

For this reason, the invention described in claim 1 is a method for producing a gas barrier film, in which a gas barrier composition is coated with a gravure roll on an inorganic oxide vapor-deposited film formed on a base film. The plate depth of engraving in the vicinity of both ends of the roll is provided symmetrically from the vicinity of the center portion of the gravure roll to the vicinity of both ends, and is shallowly formed in three stages in order of 10 to 20%.

The invention according to claim 2 is a gravure roll in which a gas barrier composition is coated on a vapor-deposited film of an inorganic oxide formed on a base film, and the gravure roll engraving plate depth is set to the gravure roll. The end portion of the gas barrier composition provided on the inorganic oxide vapor deposition film is provided so as to be symmetrical from the center portion of the substrate to the vicinity of the both end portions, and to be shallowed by 10 to 20% sequentially in three stages. It is characterized in that the amount of coating is reduced.

The invention according to claim 3 is a gas barrier property comprising the gravure roll for producing a gas barrier film by coating a gas barrier composition with a gravure roll on an inorganic oxide deposited film formed on a base film. In the film manufacturing apparatus, the gravure roll engraving plate depth is provided so as to be symmetrical from the vicinity of the center of the gravure roll to the vicinity of both ends, and gradually reduced by 10 to 20% in three stages , The coating amount of the edge part of the said gas-barrier composition apply | coated on the vapor deposition film of the said inorganic oxide is reduced, It is characterized by the above-mentioned.

According to invention of Claim 1, in the manufacturing method of the gas barrier film formed by coating the gas barrier composition with the gravure roll on the vapor deposition film of the inorganic oxide formed on the base film, the gravure roll The depth of engraving near the both ends of the gravure roll is provided symmetrically from the vicinity of the center of the gravure roll to the vicinity of both ends, and is shallowly provided in 10 steps by 10 to 20% in three steps, so that it is applied onto the deposited film of the base film. To reduce the shrinkage stress of the gas barrier composition end by reducing the coating amount of the end of the gas barrier composition to be processed, and to prevent bending of the end of the base film having an uncoated vapor deposition film Can do. Therefore, the manufacturing method of the gas barrier film which improved productivity can be provided.

According to the invention described in claim 2, onto the deposition film of an inorganic oxide is formed on the substrate film, the gravure roll coating the gas barrier composition, a plate depth of the gravure roll engraving, gravure roll The coating amount of the gas barrier composition applied on the inorganic oxide vapor-deposited film is provided so as to be symmetrical from the center to the vicinity of both ends and to become shallower by 10 to 20% sequentially in three stages . Therefore, the coating amount of the gas barrier composition edge coated on the deposited film of the base film is gradually reduced gradually toward the edge to reduce the shrinkage stress of the gas barrier composition edge. The bending of the edge part of the base film which reduces and can reduce the coating film can be prevented. Therefore, the gravure roll which manufactures the gas barrier film which improved productivity can be provided.

According to invention of Claim 3 , the gas barrier containing the gravure roll which coats a gas barrier property composition with the gravure roll on the vapor deposition film of the inorganic oxide formed on the base film, and manufactures a gas barrier film In the production apparatus of the conductive film, the gravure roll engraving plate depth is provided symmetrically from the vicinity of the center of the gravure roll to the vicinity of both ends, and is gradually reduced by 10 to 20% in three steps, and is subjected to inorganic oxidation. Since the coating amount of the end portion of the gas barrier composition applied onto the vapor deposition film of the product is reduced, the coating amount of the end portion of the gas barrier composition coated on the deposition film of the base film is directed toward the end portion. It can be gradually reduced step by step to reduce the shrinkage stress at the edge of the gas barrier composition and to prevent bending of the edge of the substrate film having an uncoated deposited film. Therefore, the manufacturing apparatus of the gas barrier film containing the gravure roll which improved productivity can be provided.

  The present invention provides a gas barrier comprising a biaxially stretched polyester film or polyamide film as a base film, and a gas barrier composition coated with a gravure roll on an inorganic oxide vapor-deposited film provided on the surface of the base film. It is a sex film. Hereinafter, the present invention will be described in detail.

  As the layer structure of the film, the gas barrier laminate film of the present invention includes, for example, a base film (10), an inorganic oxide or carbon-containing silicon oxide deposited film (20), a gas barrier, as shown in FIG. Coating film (30) and coating thin film (40). Furthermore, as shown in FIG.1 (b), you may have a surface treatment layer (10 ') and (20') on a base film (10) and a vapor deposition film (20), respectively. Moreover, as shown in FIG.1 (c), you may have a printing layer (50) on the coating thin film (40) further. Further, as shown in FIG. 1 (d), an adhesive layer (60) for dry lamination and a heat seal layer (70) may be further provided on the coating thin film (40), as shown in FIG. 1 (e). In addition, a printed layer (50) may be provided on the coating thin film (40), and an adhesive layer (60) for dry lamination and a heat seal layer (70) may be further provided on the printed layer (50). The print layer (50) may be full-surface printing or partial printing.

  The base film used in the present invention has excellent chemical or physical strength, can withstand the conditions for forming an inorganic oxide vapor-deposited film, and impairs the film characteristics of the inorganic oxide vapor-deposited film. And a biaxially stretched polyester film or polyamide film.

  Such a polyamide film may be an aliphatic polyamide, an aromatic polyamide, or a composition in which these are mixed. Specific examples of preferred polyamides include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin Lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene sebacamide (Nylon 6 · 10), Polyhexamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide (Nylon 10/6), polydecamethylene sebacamide (nylon 10/10), Polydodecamethylene dodecamide (nylon 12 and 12), metaxylenediamine-6 nylon (MXD6) and the like may be used, and a copolymer containing these as main components may be used. Examples thereof include caprolactam / Laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer And ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, and the like. It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid, esters, elastomer components with low elastic modulus, and lactams as film flexibility modifiers. is there.

  In addition to polyester resins such as polyethylene terephthalate and polyethylene naphthalate, the base film is made of polyolefin resin such as polyethylene resin or polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer ( AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl ester copolymer, polyurethane resin, Acetal-based resins, cellulose-based resins, and other various resin films can be used. In the present invention, among the above resin films, it is particularly preferable to use a polyester resin, polyolefin resin, or polyamide resin film. The base film may be any of an unstretched film of the above resin or a film stretched in a uniaxial direction or a biaxial direction.

  In the present invention, as the above-mentioned various resin films, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, and other products are used. Using the film forming method, the above-mentioned various resins can be formed into a single film, or the two or more types of various resins can be used to form a multi-layer coextrusion film. Resin is used, and various resin films are manufactured by mixing and forming a film before forming a film. If necessary, for example, a tenter method or a tubular method is used. Various types of resin films that are stretched in a uniaxial or biaxial direction can be used.

  In the present invention, the film thickness of various resin films is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm. In addition, one or more of the above-mentioned various resins are used, and when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold releasability, flame retardancy, antifungal properties, electrical characteristics, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose. And 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 also be used.

  In this invention, although the vapor deposition film | membrane of an inorganic oxide is formed in one side of the said base film, you may surface-treat a base film previously. Thereby, the adhesiveness between the base film and the vapor-deposited film of the inorganic oxide can be improved. Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and other pretreatments. is there.

  In addition, a primer coating agent, an undercoat agent, an anchor coating agent, a vapor deposition anchor coating agent, or the like can be arbitrarily applied to the surface of the base film used in the present invention in advance for surface treatment. Examples of the coating agent include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefins such as polyethylene or polypropylene. Resin or a copolymer or modified resin thereof, cellulosic resin, and other resin compositions mainly composed of a vehicle can be used.

  Among such surface treatments, it is particularly preferable to perform corona treatment or plasma treatment. For example, as plasma processing, there is plasma processing in which surface modification is performed using a plasma gas generated by ionizing a gas by arc discharge. In addition to the above, an inorganic gas such as argon gas or helium gas can be used as the plasma gas. For example, immediately before forming a vapor-deposited film of inorganic oxide by chemical vapor deposition, in-line plasma treatment removes moisture, dust, etc. on the surface of the base film, and smoothes and activates the surface. And other surface treatments can be made possible. In addition, after the inorganic oxide is deposited, plasma treatment can be performed to improve the adhesion between the deposited layer and another layer stacked thereon. Note that the plasma discharge treatment is preferably performed in consideration of the plasma output, the type of plasma gas, the supply amount of the plasma gas, the treatment time, and other conditions. Moreover, as a method for generating plasma, DC glow discharge, high frequency discharge, microwave discharge, and other devices can be used. In addition, plasma treatment can be performed by an atmospheric pressure plasma treatment method.

  Next, as the vapor deposition film of the inorganic oxide, for example, a physical vapor deposition method, a chemical vapor deposition method, or a combination thereof, a single layer film consisting of one layer of the vapor deposition film of the inorganic oxide, or two or more layers is used. It can be manufactured by forming a multilayer film or a composite film. Examples of the physical vapor deposition method in the present invention include inorganic oxides by physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition method, sputtering method, ion plating method, ion cluster beam method, etc. The deposited film can be formed. Specifically, a metal or metal oxide is used as a raw material, and a vacuum vapor deposition method in which a vaporized product is heated and vaporized on one of the base films, or a metal or metal oxide as a raw material. Used to oxidize by introducing oxygen and oxidize and deposit on one side of the base film, and further use plasma-assisted oxidation reaction deposition method that promotes oxidation reaction with plasma to form a deposited film can do. In addition, as a heating method of the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used. A method for forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 2 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, in the vacuum chamber 242 of the take-up vacuum deposition apparatus 241, the base film 201 fed out from the unwinding roll 243 in the direction of the arrow in the drawing is guided to the cooled coating drum 246 via the guide rolls 244 and 245. Is done. In the crucible 247 provided below the coating drum 246 on the substrate film 201 guided on the cooled coating drum 246, for example, the center of a deposition source 248 such as metal aluminum or aluminum oxide. A nearby surface layer surface is irradiated with an electron beam from an electron beam irradiation port of an electron beam gun (not shown), the evaporation source 248 is heated and evaporated to the upper coating drum 246 side, and further, from an oxygen gas outlet 249 if necessary. A vapor deposition film of an inorganic oxide such as aluminum oxide is formed on the substrate film 201 moving on the coating drum 246 through the masks 250 and 250 while supplying the oxygen gas or the like ejected. In physical vapor deposition such as winding on a winding roll 253 Deposited film of the inorganic oxide can be formed that. In addition, using the above-described winding-type vacuum deposition apparatus, first, a first-layer inorganic oxide deposition film is formed, and then an inorganic oxide deposition film is further formed thereon, or the above-described winding-type vacuum deposition apparatus. A vacuum evaporation apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers. Furthermore, the inorganic oxide vapor deposition film formed on the base film 201 is subjected to plasma treatment by a glow discharge plasma generator (not shown), for example, with a mixed gas of oxygen and argon, and is applied to the winding roll 253. It can also be wound up.

By the way, as a vapor deposition film of a metal or an inorganic oxide, basically, any thin film obtained by vapor deposition of a metal oxide may be used. For example, aluminum (Al), silicon (Si), magnesium (Mg), calcium ( Deposition of metal oxides such as Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) A membrane can be used. Preferably, a vapor deposition film of an oxide of a metal such as aluminum (Al) or silicon (Si) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, for example, SiO _x , AlO _x , MgO. MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. In the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). . In addition, although the film thickness of the vapor deposition film | membrane of an inorganic oxide changes with kinds etc. of the metal to be used or a metal oxide, it can select arbitrarily within the range of 50-2000 mm, for example, Preferably, it is 100-1000 mm. it can. In addition, as the inorganic oxide vapor deposition film, the metal or metal oxide to be used is used in one kind or a mixture of two or more kinds to constitute a vapor deposition film of an inorganic oxide mixed with different materials. You can also.

  Furthermore, in the present invention, an organosilicon compound may be used as a vapor deposition monomer by chemical vapor deposition. As the chemical vapor deposition method, for example, a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like can be used. Among these, it is particularly desirable to produce a film by using a low temperature plasma chemical vapor deposition method. In the present invention, specifically, on one surface of the substrate film, a film-forming monomer gas composed of one or more organic silicon compounds is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. Of carbon-containing silicon oxide composed of silicon oxide or the like using a low temperature plasma chemical vapor deposition method using oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. It can be manufactured by forming a single layer film consisting of one layer of a vapor deposition film, a multilayer film consisting of two or more layers, or a composite film. In the above, as a low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, and in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

  An example of a method for forming a vapor deposition film of carbon-containing silicon oxide by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 3 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus. The plasma chemical vapor deposition apparatus 100 of FIG. 3 winds up a base film supply chamber 110, a first film forming chamber 120 including a vacuum chamber, and a film in which a carbon-containing silicon oxide layer is formed on the base film. A winding chamber 150 is included. The base film 101 is fed out from the unwinding roll 111 disposed in the base film supply chamber 110, and the base film 101 is cooled at a predetermined speed via the auxiliary roll 121 in the first film forming chamber 120. -It conveys on the electrode drum 122 surrounding surface. Meanwhile, a vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. is supplied from a gas supply device 125, a raw material volatilization supply device 124, etc. to prepare a mixed gas composition for vapor deposition, which is used as a raw material. It is introduced into the first film forming chamber 120 through the supply nozzle 127. The mixed gas composition for vapor deposition is supplied onto the substrate film 101 transported on the circumferential surface of the cooling / electrode drum 122, and plasma is generated and irradiated by glow discharge plasma 128 to oxidize carbon-containing oxides such as silicon oxide. A deposited silicon film is formed. Subsequently, the base film 101 on which the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is transferred to the winding chamber 150 through the auxiliary roll 123 and wound up on the winding roll 151 here, the plasma chemistry is obtained. A film having a vapor-deposited film of carbon-containing silicon oxide by vapor deposition can be produced. A predetermined power is applied to the cooling / electrode drum 122 from a power source 160 disposed outside the first film forming chamber 120, and a magnet 129 is disposed in the vicinity of the cooling / electrode drum 122 to generate plasma. Occurrence is promoted. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. This glow discharge plasma is derived from one or more gas components in the mixed gas. When the substrate film is conveyed in this state, the glow discharge plasma causes the substrate on the peripheral surface of the cooling / electrode drum to be conveyed. A vapor-deposited film of carbon-containing silicon oxide such as silicon oxide can be formed on the film. In FIG. 3, reference numeral 153 represents a vacuum pump.

In the present invention, a vapor deposition film of carbon-containing silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas. Is closely bonded to one surface of the base film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide. The carbon-containing silicon oxide vapor-deposited film is a carbon-containing material represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency, barrier properties, and the like. A thin film mainly composed of a silicon oxide vapor deposition film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, and the film itself becomes yellowish. It becomes tinged and becomes less transparent.

In the present invention, the vapor-deposited film of carbon-containing silicon oxide is mainly composed of silicon oxide, and further, at least one compound of carbon, hydrogen, silicon or oxygen, or at least one compound composed of two or more elements is formed by chemical bonding or the like. It consists of the vapor deposition film to contain. 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, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the vapor-deposited film of carbon-containing silicon oxide may be varied by changing the conditions of the vapor deposition process. Under the present circumstances, as content which said compound contains in the vapor deposition film | membrane of carbon containing silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. When the content is less than 0.1% by mass, the impact resistance, spreadability, flexibility and the like of the vapor-deposited film of carbon-containing silicon oxide are insufficient, and scratches, cracks, etc. are likely to occur due to bending, etc. In some cases, it is difficult to stably maintain the barrier property. On the other hand, if it exceeds 50% by mass, the barrier property may be deteriorated.

  In the present invention, the surface of the base film is cleaned by SiOx plasma, and polar groups, free radicals, etc. are generated on the surface, so that the carbon-containing silicon oxide made of silicon oxide or the like to be formed into a film is formed. The tight adhesion between the membrane and the substrate film is high. Furthermore, in the present invention, in the vapor-deposited film of carbon-containing silicon oxide, the content of the compound may increase or decrease from the surface of the vapor-deposited film of carbon-containing silicon oxide in the depth direction. For example, in the case of decreasing from the surface in the depth direction, this improves the impact resistance and the like by the above compound on the surface of the carbon-containing silicon oxide vapor deposition film, and on the other hand, at the interface with the base film Since the content of the compound is small, the tight adhesion between the base film and the carbon-containing silicon oxide deposited film becomes strong. Such a vapor-deposited film of carbon-containing silicon oxide is not limited to the case where it is composed of one layer, and may be a multilayer film in which two or more layers are laminated, for example.

  In order to form the multilayered vapor deposition layer, it is possible to form a vapor deposition film of carbon-containing silicon oxide having different compositions by using the chemical vapor deposition apparatus 100 having a plurality of vacuum chambers as film deposition chambers. it can. FIG. 4 is used to illustrate the case of having a three-layer deposited film. The plasma enhanced chemical vapor deposition apparatus 100 of FIG. 4 includes a base film supply chamber 110, a first film forming chamber 120, a second film forming chamber 130, a third film forming chamber 140, and a carbon-containing material on the base film. A winding chamber 150 is formed for winding a film in which a silicon oxide layer is formed and stacked. In the base film supply chamber 110, the base film 101 is fed from the unwinding roll 111 to the first film forming chamber 120, and the base film 101 is cooled at a predetermined speed via the auxiliary roll 121. It is conveyed on 122 circumferential surface. In the first film forming chamber 120, a raw material volatilization supply device 124, a gas supply device 125, and the like supply a film forming monomer gas composed of one or more organic silicon compounds, oxygen gas, inert gas, and the like, The above mixed gas composition for film formation is introduced into the first film forming chamber 120 through the raw material supply nozzle 127 while adjusting the mixed gas composition for film formation composed of these, and the cooling / electrode drum 122 described above. A plasma is generated by glow discharge plasma 128 on substrate film 101 conveyed on the peripheral surface, and this is irradiated to form a first carbon-containing silicon oxide layer made of silicon oxide or the like. To do.

  The base film 101 obtained by forming the first layer carbon-containing silicon oxide film in the first film forming chamber 120 is fed to the second film forming chamber 130 through auxiliary rolls 123, 131, etc. Similarly, the base film 101 obtained by forming the carbon-containing silicon oxide film of the first layer is transported onto the peripheral surface of the cooling / electrode drum 132 at a predetermined speed. Thereafter, in the same manner as described above, 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 134, the gas supply device 135, etc. The film-forming mixed gas composition is introduced into the second film-forming chamber 130 through the raw material supply nozzle 137 while adjusting the film-forming mixed gas composition consisting of Plasma is generated by glow discharge plasma 138 on the carbon-containing silicon oxide film of the first layer of the base film 101 obtained by forming the carbon-containing silicon oxide film of the first layer conveyed on the surface. Irradiation is performed to form a second-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Furthermore, the carbon-containing silicon oxide films of the first layer and the second layer are formed in the second film forming chamber 130, and the laminated base film 101 is formed in the third film forming chamber via the auxiliary rolls 133, 141 and the like. Next, the substrate film 101 formed by forming the first layer and the second layer of carbon-containing silicon oxide film is transported onto the peripheral surface of the cooling / electrode drum 142 at a predetermined speed. Next, 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 144, the gas supply device 145, etc. The above mixed gas composition for film formation is introduced into the third film forming chamber 140 through the raw material supply nozzle 147 while adjusting the mixed gas composition, and then conveyed onto the peripheral surface of the cooling / electrode drum 142. The carbon-containing silicon oxide films of the first layer and the second layer thus formed are formed, and plasma is generated by glow discharge plasma 148 on the carbon-containing silicon oxide film of the second layer of the laminated base film 1, This is irradiated to form a third-layer carbon-containing silicon oxide film made of silicon oxide or the like.

  Next, the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are formed as described above, and the base film 101 on which these layers are stacked is placed in the winding chamber 150 via the auxiliary roll 143. Next, it is wound on a winding roll 151. Each of the cooling / electrode drums 122, 132, 142 disposed in each of the first, second, and third film forming chambers 120, 130, 140 has a first, a second, and a second, respectively. A predetermined power is applied from a power source 160 arranged outside the three film forming chambers 120, 130, and 140, and magnets 129, 139, and 149 are provided in the vicinity of the cooling / electrode drums 122, 132, and 142. To generate plasma. 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. In addition, although the above is exemplified by three layers, a film forming chamber can be arbitrarily prepared to have a multilayer structure of four or more layers.

In the above, the inside of the vacuum chamber is depressurized by a vacuum pump and adjusted to a degree of vacuum of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a degree of vacuum of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable. Further, in the present invention, regardless of whether the vapor-deposited film of carbon-containing silicon oxide is composed of a single layer or a multilayer, the degree of vacuum when forming the vapor-deposited film of carbon-containing silicon oxide such as silicon oxide is Each vacuum chamber is decompressed by a vacuum pump and adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. Since the degree of vacuum when forming a vapor-deposited film of carbon-containing silicon oxide such as silicon oxide by a conventional vacuum vapor deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the time for setting the vacuum state at the time of replacing the original film, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized. When there are a plurality of film forming chambers, the degree of vacuum may be the same or different in each chamber.

  Moreover, it is desirable that the conveyance speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 200 m / min. In plasma chemical vapor deposition, since a predetermined voltage is applied to the cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the material supply nozzle in the film forming chamber and the cooling / electrode drum. Generated. The glow discharge plasma is derived from one or more gas components contained in the film-forming mixed gas composition. When the base film is transported at a constant speed within the above range, the glow discharge plasma causes the cooling to occur. A carbon-containing silicon oxide film made of silicon oxide or the like can be uniformly formed on the base film on the electrode drum peripheral surface.

In addition, in the mixed gas composition for film formation composed of the raw material organosilicon compound, oxygen gas, and inert gas, the gas mixing ratio of each gas component is the film formation monomer gas composed of one kind of organosilicon compound. The content is preferably adjusted in the range of 1 to 40% by mass, the oxygen gas content in the range of 0.1 to 70% by mass, and the inert gas content in the range of 1 to 60% by mass. When said deposited layer is a multilayer, in each deposited layer, the ratio of the film for monomer gas and oxygen gas as the raw material (O ₂₎ may be changed respectively. As a result, the amount of carbon in the carbon-containing silicon oxide film formed can be increased or decreased. When the amount of carbon increases, the number of C—C bonds and Si—CH ₃ bonds increases, and the flexibility is high. A water-repellent carbon-containing silicon oxide film having a high barrier property against water vapor can be formed. Further, when the carbon content in the formed carbon-containing silicon oxide layer is reduced, Si—CH ₃ bonds are reduced and flexibility is inferior, but high gas barrier properties against oxygen and the like can be maintained. .

  In the present invention, the vapor-deposited film of carbon-containing silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS). The above-mentioned physical properties can be confirmed by performing analysis by performing ion etching in the depth direction and performing elemental analysis of the deposited film of carbon-containing silicon oxide.

  In the present invention, the total film thickness of the carbon-containing silicon oxide vapor-deposited film is preferably about 60 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 60 mm, it may be difficult to achieve a barrier effect. 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. Further, as a means of changing the film thickness of the carbon-containing silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. Can be done by. In the case of the multilayer structure composed of the three layers described above, the thickness of the carbon-containing silicon oxide film constituting the first layer is desirably about 20 to 200 mm, preferably about 30 to 100 mm. The film thickness of the carbon-containing silicon oxide film constituting the two layers is preferably 20 to 200 mm, preferably 30 to 100 mm, and the film thickness of the carbon-containing silicon oxide film constituting the third layer is The range of 20 to 200 mm, preferably 30 to 100 mm is desirable. 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. Further, in the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, the volume velocity of the layer is increased, that is, a method for increasing the amount of monomer gas for film formation and oxygen gas, It can be performed by a method of slowing the film forming speed.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of carbon-containing silicon oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, Vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxy Silane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

Next, in the gas barrier film of the present invention, a gas barrier coating film is further formed on the deposited film or the surface-treated surface of the deposited film. The gas barrier coating film has a general formula R ¹ _n M (OR ² ). _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents an integer of 1 or more) N + m represents the valence of M.) and contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and a sol-gel. A coating film comprising a gas barrier composition obtained by polycondensation by a sol-gel method in the presence of a process catalyst, acid, water, and an organic solvent, and the deposited film formed on the substrate film On top of the coating film It can be formed by heat treatment for 2 seconds to 10 minutes at a temperature of 20 ° C. to 200 ° C. and below the melting point of the base film.

Further, the gas barrier composition is applied onto the carbon-containing silicon oxide vapor-deposited film on the base film, and two or more coating films are stacked, and the temperature of the base film is 20 ° C. to 200 ° C. You may heat-process for 2 second-10 minutes at the temperature below melting | fusing point, and may form the composite polymer layer which laminated | stacked two or more gas barrier coating films. As the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.
In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned. In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 4 which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and the like. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different. Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.

In the present invention, silicon is preferable. In this case, as an alkoxide that can be preferably used in the present invention, when n = 0 in the general formula R ¹ _n M (OR ² ) _m , the general formula Si (ORa) ₄ (wherein Ra is Represents an alkyl group having 1 to 5 carbon atoms). In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Specific examples of such an alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si ( OC ₄ H ₉₎ can be exemplified ₄ like. In the case where n is 1 or more, the general formula RbnSi (ORc) _4-m (wherein m represents an integer of 1, 2, 3 and Rb and Rc are a methyl group, an ethyl group, An alkylalkoxysilane represented by n-propyl group, n-butyl group, etc.) can be used. Examples of such an alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH). _{3) 2,} dimethyl diethoxy silane _{(CH 3) 2 Si (OC} 2 H 5) 2, may use other like. In the present invention, the above alkoxysilane, alkylalkoxysilane and the like may be used alone or in combination of two or more. In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

In the present invention, a zirconium alkoxide in which M is Zr can also be suitably used as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m . For example, tetramethoxy zirconium Zr (OCH _{3) 4,} tetraethoxy zirconium _{Zr (OC 2 H 5) 4} , tetra i propoxy zirconium _{Zr (iso-0C 3 H 7} ) 4, tetra-n-butoxy zirconium Zr (OC ₄ H _{9) 4} etc. can be illustrated.

Further, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , a titanium alkoxide in which M is Ti can be preferably used. For example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetra Examples thereof include ethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (iso-0C ₃ H ₇ ) ₄ , tetra n-butoxytitanium Ti (OC ₄ H ₉ ) ₄ , and the like. As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , an aluminum alkoxide in which M is Al can be used. For example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum _{Al (OC 2 H 5) 4} , tetraisopropoxy aluminum _{Al (is0-OC 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (OC 4 H 9) 4} , may use other like.

  In the present invention, two or more of the alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness, heat resistance and the like of the resulting gas barrier laminate film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Under the present circumstances, the usage-amount of a zirconium alkoxide is the range of 10 mass parts or less with respect to 100 mass parts of said alkoxysilanes. When the amount exceeds 10 parts by mass, the formed gas barrier coating film tends to gel, and the brittleness of the film increases, and the gas barrier coating film tends to peel off when the base film is coated. This is not desirable. In addition, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the resulting gas barrier coating film is lowered, and the heat resistance is remarkably improved. Under the present circumstances, the usage-amount of a titanium alkoxide is the range of 5 mass parts or less with respect to 100 mass parts of said alkoxysilane. When the amount exceeds 5 parts by mass, the brittleness of the formed gas barrier coating film increases, and the gas barrier coating film may be easily peeled off when the base film is coated.

  As the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer used in the present invention, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, respectively, or polyvinyl alcohol A single resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved by using a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer. When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0. It is preferable that the position is from 05 to 10: 6.

The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by mass, preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total amount of the alkoxide. The blending ratio of When it exceeds 500 parts by mass, the brittleness of the gas barrier coating film becomes large, and the water resistance and weather resistance of the resulting barrier film may be lowered. On the other hand, if it is less than 5 parts by mass, the gas barrier property may be lowered.
In the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, as the polyvinyl alcohol resin, one obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited. Examples of such a polyvinyl alcohol resin include “RS-110 (degree of saponification = 99%, degree of polymerization = 1,000)” manufactured by Kuraray Co., Ltd., and “Kuraray Poval LM-20SO ( “Saponification degree = 40%, polymerization degree = 2,000)”, “GOHSENOL NM-14 (degree of saponification = 99%, polymerization degree = 1,400)” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Can do.

  As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. In addition, the content of the repeating unit derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable. Examples of such an ethylene / vinyl alcohol copolymer include “Eval EP-F101 (ethylene content; 32 mol%)” manufactured by Kuraray Co., Ltd., “Soarnol D2908 (ethylene content; 29 mol) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.” %) "And the like.

The gas barrier composition used in the present invention has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) And a polycondensation by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. Gas barrier composition. In preparing the gas barrier composition, a silane coupling agent or the like may be added.

  As the silane coupling agent that can be suitably used in the present invention, known organic reactive group-containing organoalkoxysilanes can be widely used. For example, an organoalkoxysilane having an epoxy group is suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- (3,4-epoxy). (Cyclohexyl) ethyltrimethoxysilane or the like can be used. Such silane coupling agents may be used alone or in combination of two or more. In addition, the usage-amount of a silane coupling agent exists in the range of 1-20 mass parts with respect to 100 mass parts of said alkoxysilanes. If 20 parts by mass or more is used, the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulation and workability of the gas barrier coating film may be lowered.

  The sol-gel catalyst is a catalyst mainly used as a polycondensation catalyst, and a basic substance such as a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. . For example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, etc. can be used. In the present invention, N, N-dimethylbenzylamine is particularly preferred. The usage-amount is 0.01-1.0 mass part per 100 mass parts of total amounts of an alkoxide and a silane coupling agent.

  The “acid” used in the gas barrier composition is mainly used as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or the like in the sol-gel method. For example, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like can be used. The amount of the acid used is preferably 0.001 to 0.05 mol based on the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety).

  Furthermore, in said gas barrier composition, water of 0.1-100 mol with respect to 1 mol of total molar amounts of said alkoxide, Preferably, the ratio of 0.8-2 mol can be used. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to become a low-density, porous polymer, Such a porous polymer cannot improve the gas barrier property of the gas barrier laminate film. Moreover, when the amount of the water is less than 0.8 mol, the hydrolysis reaction may hardly proceed.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, it is preferable to use n-butanol. An ethylene / vinyl alcohol copolymer solubilized in a solvent can also be used. For example, trade name “Soarnol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be preferably used. The amount of the organic solvent used is usually 30 with respect to 100 mass of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel method catalyst. It is -500 mass parts.

In the present invention, the gas barrier laminate film can be produced by the following method.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, an acid, water, an organic solvent, and, if necessary, A metal alkoxide or the like is mixed to prepare a gas barrier composition. By mixing, the gas barrier composition (coating liquid) starts and proceeds with a polycondensation reaction. Next, the above gas barrier composition is applied onto the vapor-deposited film of carbon-containing silicon oxide on the base film and dried by a conventional method. By this drying step, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. . On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

  Next, the base film coated with the gas barrier composition is heated at 20 ° C. to 200 ° C. and a temperature below the melting point of the base film, preferably at a temperature in the range of 100 ° C. to 200 ° C. for 2 seconds to 10 minutes. Process. Thus, a gas barrier laminated film in which one or more gas barrier coating films of the gas barrier composition are formed on the carbon-containing silicon oxide vapor deposition film can be produced. A gas barrier laminate film obtained using an ethylene / vinyl alcohol copolymer alone or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer is excellent in gas barrier properties after hydrothermal treatment. On the other hand, when a gas barrier laminate film is produced using only a polyvinyl alcohol-based resin, a first coating film is formed by previously applying a gas barrier composition using a polyvinyl alcohol-based resin, A gas barrier composition containing an ethylene / vinyl alcohol copolymer is applied onto the coating film to form a second coating film, and a composite layer thereof is formed. A gas barrier laminate film with improved properties can be produced. Further, a coating film is formed by the gas barrier composition containing the ethylene / vinyl alcohol copolymer, or a gas barrier composition containing a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. Even if a film is formed and a plurality of these films are laminated, it becomes an effective means for improving the gas barrier property of the gas barrier laminated film according to the present invention.

  The production method of the gas barrier laminate film used in the present invention will be described in more detail using alkoxysilane as the alkoxide. The alkoxysilane and metal alkoxide blended as the gas barrier composition are hydrolyzed by the added water. During the hydrolysis, the acid acts as a hydrolysis catalyst. Next, protons are taken from the hydroxyl groups generated by hydrolysis by the action of the sol-gel method catalyst, and the hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.

  In addition, the opening of the epoxy group also occurs due to the action of the base catalyst, generating a hydroxyl group. In addition, a polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. In the reaction system, polyvinyl alcohol resin, ethylene / vinyl alcohol copolymer, or polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer are present, so polyvinyl alcohol resin and ethylene / vinyl alcohol copolymer are present. Reaction with the hydroxyl group of the polymer also occurs. In addition, the polycondensate to be generated includes, for example, an inorganic part composed of a bond such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part resulting from the silane coupling agent. It is a composite polymer containing.

  In the above reaction, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from a silane coupling agent is first formed.

  This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer. This OR group is hydrolyzed to become an OH group using the existing acid as a catalyst. The OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds. To do. That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II) to form Si—O—Si. For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) is formed.

  The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition increases during preparation. When this gas barrier composition is applied on the vapor-deposited film of carbon-containing silicon oxide on the base film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation reaction is completed. A transparent coating film is formed on the deposited carbon-containing silicon oxide film. In addition, when laminating | stacking two or more said coating films, the composite polymer in the coating film of an interlayer is also condensed, and a layer couple | bonds firmly between layers.

  Furthermore, the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the base film or the hydroxyl group on the surface of the vapor-deposited film of carbon-containing silicon oxide on the base film. The adhesion between the material film or the surface of the carbon-containing silicon oxide vapor deposition film and the coating film is also good. Thus, in the present invention, the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordinate bond by a hydrolysis / co-condensation reaction. The adhesion between the vapor-deposited film of carbon-containing silicon oxide and the gas barrier coating film is improved, and a better gas barrier effect can be exhibited by the synergistic effect of the two layers. In the present invention, when the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.0 to 1.7 mol, relative to 1 mol of alkoxides, the above linear polymer is used. Is formed.

Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Since the rigidity is also high, it is particularly excellent in gas barrier properties (blocking and blocking permeation of O ₂ , N ₂ , H ₂ O, CO ₂ , etc.). In particular, when used for so-called gas-filled packaging filled with N ₂ , CO ₂ gas, etc., the excellent gas barrier property is extremely effective for holding the filled gas. Furthermore, the gas barrier laminate film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.

  As a method of applying the gas barrier composition, for example, a roll coating such as a gravure roll coater, spray coating, spin coating, dipping, brush, barcode, applicator or the like, one or more times. By coating, a coating film having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed. Further, under a normal environment, 50 to 300 ° C., preferably 70 to Condensation is performed by heating and drying at a temperature of 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier coating film of the present invention can be formed.

  Here, a method of coating the gas barrier composition on the inorganic oxide film formed on the base film 201, which is a feature of the present invention, will be described with reference to FIG. 5 and FIGS. 5 is a schematic configuration diagram showing an example of a winding-type vacuum vapor deposition apparatus having a gas barrier composition coating process, FIG. 6 is a schematic front view of a gravure roll, and FIG. 7 is a surface of the gravure roll. The enlarged front schematic diagram is shown. First, the base film 201 taken up by the take-up roll 253 in the vacuum chamber 242 in the take-up vacuum deposition apparatus 241 is transferred into the chamber 301 of the next step which is the coating step 300 of the gas barrier composition. The barrier coating liquid, which is a gas barrier composition prepared in advance in the container 302, is coated on the inorganic oxide vapor-deposited film of the base film 201 using the gravure roll 303.

  At this time, as shown in FIG. 6, the gravure roll 303 surface engraving is made symmetrical, for example, with the plate depth of the portion of width A, which is near the center 304, being 40 μm and from the width A toward both ends 305. The plate depth of the portion of the left and right width B provided 20 mm each outside the width A adjacent to the width A is 33 μm, and further symmetrically adjacent to the width B from the width B toward the both ends 305. The plate depth is gradually decreased from the vicinity of the center 304 toward the vicinity of both ends 305 so that the plate depth of the portion of the left and right width C provided by 20 mm each outside B is 27 μm. Is provided with gradation. The gravure roll 303 is not engraved in the vicinity 305 of both ends. Note that the gravure roll 303 is not limited to the above-described plate depth. For example, the plate depth of the left and right width B portion may be 36 μm, and the plate depth of the left and right width C portion may be 30 μm. It is preferable to provide the plate depth shallower by 10 to 20% in the order of the lateral width C.

  In this way, the gravure roll engraving depth is provided symmetrically in three steps from the vicinity of the center of the gravure roll to the vicinity of both ends, so that the gravure roll is shallowly formed in three stages. Reduce the shrinkage stress at the edge of the coated gas barrier composition by gradually reducing the amount of coating at the edge of the gas barrier composition to be coated toward the deposited film edge of the base film. Further, it is possible to prevent bending of the end portion of the base film having a vapor deposition film that is not coated with the gas barrier composition.

The base film 201 in which the barrier coating liquid 302 made of the gas barrier composition is coated on the inorganic oxide vapor-deposited film is dried by heat treatment, and then taken up by the take-up roll 306. Note that, as the above operating conditions, the degree of vacuum in the vapor deposition chamber in the vacuum chamber 242: 2.0 × 10 ⁻⁴ mbar, the power of the electron beam: 25 kW, the conveyance speed of the base film 201: 240 m / min, heat treatment However, it is not limited to these numerical values, and the operating conditions are appropriately changed according to various conditions.

  The coating thin film by the polyurethane resin composition of the present invention is formed on the gas barrier coating film or its surface treatment layer by a polyurethane resin composition containing a silane coupling agent and a filler. Also good. As the silane coupling agent used for the coating thin film, bifunctional organofunctional silane monomers can be used, for example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane. , Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ -Mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β -Hide Kishiechiru)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl silicone - can be used one or more of the aqueous solution or the like of the emission.

  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 the barrier coating. Silane coupling occurs on the barrier coating film by causing a reaction such as a reaction such as dehydration condensation reaction with silicon contained in the film or an active group on the barrier coating film, for example, a functional group such as a hydroxyl group. The agent is modified with a covalent bond or the like, and further, a strong bond is formed by adsorption of the silanol group itself onto the barrier coating film or hydrogen bond. On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto on the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. For example, an adhesive layer for laminating It reacts with substances constituting the anchor coat layer and other layers to form a strong bond. As a result, in the present invention, the barrier coating film and the heat-sealable resin layer are firmly and closely bonded via the adhesive bond layer, the anchor coat layer, and the like by the chemical bond as described above. Strength can be increased and a strong laminated structure with high laminate strength can be formed. In particular, in the present invention, a monomer for depositing an organic silicon compound is used to form a vapor-deposited film of carbon-containing silicon oxide, but the organosilicon compound such as tetraethoxysilane used for forming the vapor-deposited film is applied to the gas barrier coating. Since the silane coupling agent is used in common for the gas barrier coating film and the coating thin film, each thin film is strongly bonded to each other by containing the components in common. Conceivable. In particular, by laminating a coating layer containing a silane coupling agent, adhesion between the gas barrier coating film and the laminating adhesive layer or anchor coat layer is ensured, and thus laminated on these. Adhesion with the heat seal layer is also ensured, and laminate strength and the like are improved.

  As the filler, for example, calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and others can be used. This is to improve the coating suitability and the like of the polyurethane resin composition by adjusting the viscosity and the like.

  Specific examples of the polyurethane-based resin include a polymer obtained by reaction of a polyfunctional isocyanate and a hydroxyl group-containing compound, specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene. Polyfunctional isocyanates such as aromatic polyisocyanates such as polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and polyether polyols, polyester polyols, polyacrylate polyols, etc. One-pack or two-pack polyurethane resins obtained by reaction with a hydroxyl group-containing compound can be used. Thus, in the present invention, by using the polyurethane-based resin as described above, the degree of elongation of the coating thin film is improved, and the post-processing suitability such as laminating or bag making is improved. It prevents the occurrence of cracks in the thin film of inorganic oxide during processing.

  As said polyurethane-type resin composition, a silane coupling agent, about 0.05-10 mass% with respect to a polyurethane-type resin, 1-30 mass%, Preferably, about 0.1-5 mass%, a filler Add about 0.1 to 20% by mass, preferably about 1 to 10% by mass, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. Is added arbitrarily, a solvent, a diluent, etc. are added and mixed well to prepare a polyurethane resin composition. Thus, in the present invention, the polyurethane resin composition as described above is applied onto the inorganic oxide thin film by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods. After coating, the coating film is dried to remove the solvent, diluent, etc., and the coating thin film according to the present invention can be formed. In addition, in this invention, as a film thickness of the coating thin film by a polyurethane-type resin composition, about 0.01-50 micrometers, for example, Preferably, about 0.1-5 micrometers is desirable.

  Next, as a laminating adhesive, a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose Adhesive, polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reaction Type (meth) acrylic acid adhesive, chloroprene rubber, ni Rirugomu, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide It can act and improve processing aptitude, such as lamination processing and printing processing, and can avoid generation of a crack etc. to a barrier thin film layer which consists of inorganic oxides. The laminate adhesive layer made of the above-mentioned laminate adhesive preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like. The amount of the laminating adhesive is not particularly limited, but is generally 0.1 to 10 g / m ² (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

  A desired printed pattern layer can be formed between any layers forming the gas barrier film. As the printed pattern layer, for example, a normal gravure ink composition, an offset ink composition, a relief printing ink composition, a screen ink composition, and other ink compositions are used on the primer layer. , Gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, by forming a desired printing pattern consisting of characters, figures, patterns, symbols, etc. be able to.

  Regarding the ink composition, examples of the vehicle constituting the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, and polyvinyl acetate. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resins, polyamide resins, alkyd resins, epoxy resins, unsaturated polyester resins, thermosetting poly (meth) acrylic resins, melamine resins, urea resins, polyurethane resins, phenol resins, xylene resins , Maleic resin, Fiber resins such as rocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more of fats and oils and other resins can be used.

  In the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of coloring agents such as dyes and pigments are added to this, and if necessary, a filler, Light stabilizers such as additives, plasticizers, antioxidants, UV absorbers, dispersants, thickeners, drying agents, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added, solvent, dilution Ink compositions having various forms obtained by sufficiently kneading with an agent or the like can be used. The print layer may be printed by surface printing or reverse printing of a desired printing pattern such as a character, a figure, a symbol, a pattern, or a pattern, and may be full surface printing or partial printing.

  In the present invention, a heat seal can be laminated on the vapor deposition layer by extrusion. When the heat seal layer is formed by extrusion, the heat seal layer is preferably formed on the vapor deposition layer via an anchor coating agent. Examples of the anchor coating agent to be used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients.

According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide Acting, improving processability such as laminating and printing, avoiding the occurrence of cracks in the barrier thin film layer made of inorganic oxide, and tight adhesion between the barrier film and the heat seal layer And the occurrence of cracks in the barrier thin film layer made of an inorganic oxide can be prevented, and the laminate strength can be improved. In the present invention, the anchor coating agent is coated by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and the solvent, diluent or the like is dried, and the anchor according to the present invention is applied. An anchor coating agent layer with a coating agent can be formed. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). Moreover, it is preferable that the anchor coating agent layer which consists of said anchor coating agent has a tensile elongation degree of 100 to 300% based on JIS specification K7113.

  As the heat seal layer that can be laminated on the gas barrier film of the present invention, polyolefin resins having various heat seal properties that can be melted by heat and fused to each other can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resin, one or more films made of a resin such as polyvinyl chloride resin or sheet or coated film and the like can be used. The heat seal layer may be a single layer or a multilayer composed of one of the above resins, and the thickness of the heat seal layer is 15 to 130 μm. If the thickness is less than 15 μm, scratches and cracks may occur in the deposited film of carbon-containing silicon oxide.

  A molded product can be produced using the gas barrier film of the present invention. For example, a primer layer, a laminating adhesive layer, and a heat seal layer may be further laminated on the gas barrier film of the present invention to form a laminated material, whereby a packaging container can be obtained. For example, the surface of the heat sealable film of the inner layer of the laminated material is faced and folded, or two of them are overlapped, and the peripheral end portion is further heat sealed to provide a seal portion to form a bag body Can be configured. As the bag making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side seal type, two-side seal Heat seal by heat seal type such as mold, three-side seal type, four-side seal type, envelope sticker seal type, palm seal sticker type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Thus, various types of packaging containers according to the present invention 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 a laminated material.

  As a heat sealing method, for example, known methods such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used. In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or an opening / closing zipper can be arbitrarily attached to the packaging container as described above. Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

  Such packaging containers are used for filling and packaging various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, and other articles.

  Next, the present invention will be specifically described with reference to examples, but these examples do not limit the present invention.

Example 1
The vacuum degree in the deposition chamber was reduced to 2.0 × 10 ⁻⁴ mbar and the vacuum degree in the take-up chamber was reduced to about 2.0 × 10 ⁻² mbar. A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm having a corona-treated surface on one side is fed out at a conveyance speed of 240 m / min, and a crucible mounted on an electron beam physical vapor deposition apparatus is provided on the corona-treated surface of the biaxially stretched polyethylene terephthalate film. The aluminum was evaporated by irradiating an electron beam with an electric power of 25 kw while supplying oxygen gas to the aluminum contained in the aluminum, and on the corona-treated surface of the biaxially stretched polyethylene terephthalate film guided on the coating drum, Film thickness of 200 mm with evaporated aluminum To form a deposited film of aluminum oxide. Next, a preliminarily prepared hydrolyzate of composition b was added to the mixed solution of composition a prepared according to the composition shown in Table 1 and stirred to obtain a colorless and transparent barrier coating solution.

  Then, the barrier coating liquid made of the gas barrier composition prepared above is coated on the vapor deposition surface of the aluminum oxide in the polyethylene terephthalate film using the gravure roll provided with gradation in the plate depth described above, and then the drying temperature of 180 A gas barrier base material having a gas barrier coat layer having a thickness of 0.3 μm in a dried state was formed by heat treatment at a temperature of 100 ° C. and a conveyance speed of 100 m / min.

Example 2
The degree of vacuum in the vacuum chamber is reduced to 2-6 × 10 ⁻⁶ mbar and the degree of vacuum in the deposition chamber is reduced to about 2-5 × 10 ⁻³ mbar. A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which is mounted on a feed roll and having a corona-treated surface on one side, is fed out at a conveyance speed of 100 m / min. While supplying siloxane / oxygen gas / helium, the power supplied to the electrode drum was cooled to 10 kW, and a silicon oxide vapor deposition film having a thickness of 120 mm was formed on the corona-treated surface of the biaxially stretched polyethylene terephthalate film by glow discharge plasma. . Next, plasma treatment is performed on the surface of the silicon oxide deposition film by glow discharge plasma at a power of 9 kW, a mixed gas pressure of 6 × 10 ⁻⁵ torr, and a transfer speed of 420 m / min using a mixed gas of oxygen gas / argon gas. Then, a plasma-treated surface was formed in which the surface tension of the deposited silicon oxide film surface was improved to 54 dyn / cm or more. Next, after coating the plasma-treated surface with a barrier coating solution having the composition shown in Table 1 using a gravure roll having gradation in the plate depth, heat treatment was performed at a drying temperature of 180 ° C. and a conveyance speed of 100 m / min. Thus, a gas barrier substrate having a gas barrier coat layer having a thickness of 0.3 μm in a dry state was formed.

Example 3
A gas barrier substrate was formed in the same manner as in Example 1 except that the gas barrier coat layer was provided in a dry state with a thickness of 0.5 μm.

Example 4
The barrier substrate having the gas barrier coat layer obtained in Example 1 was further subjected to vapor deposition of aluminum oxide and coating with a barrier coating solution in the same manner as in Example 1 to form a gas barrier substrate.

Example 5
The barrier substrate having the gas barrier coat layer obtained in Example 2 was further vapor-deposited with silicon oxide and coated with a barrier coating solution in the same manner as in Example 2 to form a gas barrier substrate.

Example 6
The barrier substrate having the gas barrier coat layer obtained in Example 2 was further subjected to vapor deposition of aluminum oxide and coating with a barrier coating solution in the same manner as in Example 1 to form a gas barrier substrate.

Comparative Example 1
A gas barrier substrate was formed in the same manner as in Example 1 except that the barrier coating liquid was coated on the aluminum oxide vapor deposition surface using a conventional gravure roll and heat-treated at a drying temperature of 140 ° C.

Comparative Example 2
A gas barrier substrate was formed in the same manner as in Example 3 except that the barrier coating liquid was coated on the aluminum oxide vapor deposition surface using a conventional gravure roll and heat-treated at a drying temperature of 140 ° C.

Comparative Example 3
A gas barrier substrate was formed in the same manner as in Example 1 except that the vapor deposition surface of aluminum oxide was coated with a conventional gravure roll and the barrier coating solution was coated.

Comparative Example 4
A gas barrier substrate was formed in the same manner as in Example 4 except that a barrier coating solution was coated on the aluminum oxide deposition surface using a conventional gravure roll and heat-treated at a drying temperature of 140 ° C.

Evaluation Method Gas barrier properties were evaluated using the gas barrier substrates produced in Examples 1 to 6 and Comparative Examples 1 to 4. This gas barrier property was evaluated by oxygen permeability and water vapor permeability. The results are shown in Table 1. The oxygen permeability was measured with a measuring instrument (model name, OX-TRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. The water vapor permeability was measured with a measuring instrument (model name, PERMATRAN 3/31) manufactured by MOCON, USA under the conditions of a temperature of 40 ° C. and a humidity of 100% RH. In Table 1, the unit of oxygen permeability is [cc / m ² / day · 23 ° C. · 90% RH], and the unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90 % RH].

Results (1) From the above examples and comparative examples, the deposited film is not limited to an inorganic oxide such as aluminum oxide by physical vapor deposition or an organic silicon compound such as silicon oxide by chemical vapor deposition. Is a single-layer film consisting of one layer of vapor-deposited films of inorganic oxide and organic silicon compound, a multilayer film consisting of two layers, a composite film of these inorganic oxides and organic silicon compounds, or a vapor-deposited film of inorganic oxide Even if the thickness of the coating layer by the barrier coating solution on the single layer film is increased to 0.5 μm, the barrier coating solution is coated on the deposition surface of the base film using a gravure roll provided with gradation in the plate depth ( From Examples 1 to 6, it was found that the end of the film not coated with the barrier coating solution did not break. Moreover, even if the conventional gravure roll is used, after the barrier coating liquid is coated on the vapor deposition surface of the base film, the above-described ear breakage occurs by setting the drying temperature to a lower 140 ° C. (Comparative Example 1). It also turned out not to be.

  (2) In Comparative Example 1, the edge of the film not coated with the barrier coating solution does not break, but because of the low drying temperature, the oxygen permeability and water vapor permeability are large, and the gas barrier property is low. It has been found.

  Therefore, in the film forming conditions in Examples 1 to 6, while coating the barrier coating liquid on the deposition surface of the base film using a gravure roll provided with gradation in the plate depth, while ensuring gas barrier properties, The coating amount of the gas barrier composition edge coated on the vapor deposition film of the base film is gradually decreased gradually toward the edge to reduce the shrinkage stress at the gas barrier composition edge, and the coating is performed. It has been found that the edge of the base film film having an undeposited film can be prevented from breaking.

  The method and apparatus for producing a gas barrier film according to the present invention, in particular, ensures gas barrier properties by coating the vapor deposition surface of the base film with a barrier coating solution using a gravure roll having gradation in the plate depth. On the other hand, it is useful for preventing the edge breakage of the end of the base film having an uncoated vapor deposition film and improving the productivity of the gas barrier film.

(A)-(e) is a cross-sectional view explaining an example of the gas barrier laminated film of this invention. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of the low temperature plasma chemical vapor deposition apparatus which has a some film forming chamber. It is a schematic block diagram which shows an example of the winding-type vacuum evaporation apparatus which has a coating process of a gas barrier property composition. It is a front schematic diagram of a gravure roll. It is the front schematic diagram which expanded the surface of the gravure roll.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base film 10 'Plasma surface treatment surface 20 Deposition film of inorganic oxide or carbon-containing silicon oxide 20' Corona surface treatment surface 30 Gas barrier coating film 40 Coating thin film 50 Printing layer 60 Adhesive layer for laminating 70 Heat seal layer 100 Plasma chemical vapor deposition apparatus 241 Winding type vacuum deposition apparatus 300 Gas barrier composition coating process 301 Chamber 303 Gravure roll 304 Near central part 305 Near both end parts 306 Winding roll A, B, C Width

Claims (3)

In a method for producing a gas barrier film comprising a gas barrier composition coated with a gravure roll on an inorganic oxide vapor-deposited film formed on a base film, the engraving plate depth in the vicinity of both ends of the gravure roll is determined. A method for producing a gas barrier film, characterized in that the gravure roll is provided symmetrically from the vicinity of the center of the gravure roll to the vicinity of both ends and shallowly in three stages in steps of 10 to 20% . In a gravure roll that coats a gas barrier composition on a vapor deposition film of an inorganic oxide formed on a base film, the gravure roll engraving depth is changed from the vicinity of the center of the gravure roll to the vicinity of both ends. It is provided so as to be symmetrical in the left and right direction and gradually become shallower by 10 to 20% in three stages, and the coating amount of the end portion of the gas barrier composition applied on the vapor-deposited film of the inorganic oxide is reduced. A gravure roll. In the gas barrier film manufacturing apparatus including the gravure roll, a gas barrier film is manufactured by coating a gas barrier composition with a gravure roll on an inorganic oxide vapor-deposited film formed on a base film. The engraving plate depth is provided so as to be symmetrical from the center of the gravure roll toward the ends of the gravure roll , and to become shallower in steps of 10 to 20% in three stages. An apparatus for producing a gas barrier film containing a gravure roll, wherein an application amount of an end portion of the gas barrier composition to be applied is reduced.

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