JP5359079B2 - Gas barrier packaging material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier packaging material excellent in coloration resistance. <P>SOLUTION: The gas barrier packaging material is formed by laminating a base material layer, adhesive layer, gas barrier layer, anchor coat layer and polyolefin resin layer. The anchor coat layer is formed by coating and drying an aqueous dispersion of what a polyolefin copolymer resin containing an unsaturated carboxylic acid or its anhydride in the range of 0.01-5 mass% is dispersed into 1 &mu;m or smaller in terms of the number average particle size. The polyolefin resin layer is characterized in that the surface contacting with the anchor coat layer is ozone-treated. The ozone treatment can impart the coloration resistance and improve the lamination strength. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a gas barrier packaging material capable of preventing coloring of a packaging material even when the content of the coloring material is a content, and relates to ozone in a polyolefin resin layer that is melt-extruded into an anchor coat layer constituting the packaging material. The present invention relates to a gas barrier packaging material capable of preventing coloring by performing the treatment, and a method for producing a gas barrier packaging material capable of improving production efficiency by ozone treatment.

  As packaging materials for foods, electronic parts and the like, there are films in which a gas barrier layer and a heat seal layer are laminated on a plastic base film, and packaging containers made into bags such as gusset types and pillow types are frequently used.

  Packaging materials and packaging containers containing such plastic materials are imparted with various characteristics according to their use and are used in many ways. As such characteristics, for example, returnable containers have been developed for the purpose of reusing packaging materials and packaging containers containing plastic materials. Aimed at imparting non-coloring and non-odorizing properties for reuse, aliphatic having a lactic acid monomer unit in the molecule and a lactic acid monomer component content of 50% by weight or more It is a returnable container for foods made of a polyester polymer and having non-coloring properties and / or non-odorizing properties (Patent Document 1). Biodegradable plastics may be colored when they come into contact with foods, etc., and have been made in view of the fact that they are not suitable materials for repeated use, and specify the minimum content of lactic acid monomer components. This ensures the non-coloring property.

  Also, as an alcohol-resistant gas barrier film, a packaging bag for packaging a liquid having an alcohol concentration of 50% by mass or more, or an impregnated product of the liquid, and a heat seal layer is extruded on the barrier layer and laminated by a laminating method. In this case, there is a packaging bag for alcohol-containing materials, characterized in that an anchor coat agent having a specific composition is coated (Patent Document 2). When the alcohol concentration is 50% by mass or more, the alcohol component penetrates into the laminate during long-term storage, and particularly the adhesive layer between the barrier layer and the heat seal layer. This has been made in view of the fact that delamination may occur. If an adhesive for dry lamination is used for laminating the barrier layer and the heat seal layer, it is necessary to use an organic solvent at the time of application, which has a large environmental impact, and if an extrusion lamination method is adopted for laminating the heat seal layer The conventional polyethyleneimine-based AC agent or the like has insufficient alcohol resistance when it contains a high concentration of alcohol. However, an aqueous dispersion in which a polyolefin copolymer resin containing an unsaturated carboxylic acid or anhydride thereof in an amount of 0.01 to 5% by mass as an AC agent is dispersed to a number average particle diameter of 1 μm or less without using a non-volatile aqueous additive, It can prevent delamination.

In Patent Document 2, a packaging body using an aluminum foil as a barrier layer and a random copolymer of ethylene-methacrylic acid as a heat seal layer prevents delamination even when contents containing alcohol are packaged. Although there is a problem that the tearability of the package is lowered, the predetermined AC agent improves the tearability.
JP 2000-119377 A JP 2008-94471 A

  Conventionally, coloring foods such as kimchi and curry are colored on the packaging material by use, and this coloring cannot be easily removed by a dishwashing detergent or the like. When the content contains a coloring component, the plastic layer such as the heat seal layer is generally colored, and particularly frequently occurs on the innermost layer side of the packaging material in direct contact with the content. This coloring is one factor that hinders the reuse of packaging materials.

  The above-mentioned Patent Document 1, which provides a technique relating to color resistance, is intended to provide a non-colorable food returnable container, which is originally intended for biodegradable polylactic acid as a plastic substrate, It is not intended for other plastic materials. Therefore, even when using plastic materials other than biodegradable plastics, development of a gas barrier packaging material having coloring resistance is desired.

  Further, if the gas barrier layer and the heat seal layer can be laminated by extrusion lamination as a packaging material, the solvent used for the dry lamination adhesive does not remain in the heat seal layer, which is excellent in safety. As such a packaging material, there is a packaging bag for an alcohol-containing material of Patent Document 2, but it may contain a coloring component together with alcohol, but Patent Document 2 describes the delamination of a gas barrier layer and a heat seal layer. There is no description regarding coloration resistance. Therefore, it is desired to develop a gas barrier packaging material that can be laminated by extrusion lamination with a gas barrier layer and a heat seal layer and that has coloration resistance.

  In addition, the color of the packaging material colored with the colorable substance is not necessarily the same as the color of the colorable substance, and may have a different color depending on the components constituting the plastic film. Accordingly, it is desired to develop a gas barrier packaging material that can prevent coloring due to the coloring component even when not intended for reuse.

  Furthermore, as the gas barrier layer, there are a gas barrier laminated film or an aluminum foil on which an inorganic oxide or the like is vapor-deposited, and a transparent vapor-deposited film is suitable for confirming the contents. Can be secured. Therefore, even when both a transparent vapor deposition film and an aluminum foil are used as a gas barrier layer, it is desired to develop a gas barrier packaging material having excellent coloring resistance.

  Furthermore, spices such as curry powder, kimchi element (powder), and chili as contents may be opened through a notch or the like during use, and are required to have excellent hand cutting properties. Conventional AC agent and no-anchor EMAA specification packaging bags have reduced laminar strength due to delamination between the barrier layer and the heat seal layer, and the hand tearability may also be reduced accordingly. In particular, spices such as curry powder and kimchi are prone to delamination, and even when such spices are used as contents, the gas barrier has sufficient coloring resistance and can be ensured without reducing the strength of the lamination. Development of a packaging material is desired.

  Furthermore, since the packaging material is used for various applications, it is required to have excellent production efficiency. Therefore, a method for producing a packaging material that is excellent in production efficiency during production is desired.

  As a result of examining the packaging material in which the heat seal layer is laminated on the gas barrier layer by the extrusion lamination method, the present inventors have used a predetermined AC agent, and further, a polyolefin-based resin layer that is melt-extruded into the AC agent layer. When the surface is subjected to ozone treatment, it is excellent in coloring resistance and laminate strength. Therefore, it can be suitably used for storing spices and coloring contents, and further, the AC agent layer of the polyolefin resin layer to be melt-extruded. The present invention has been completed by finding that a gas barrier packaging material having excellent color resistance and laminate strength can be produced by performing ozone treatment on the surface in contact with the substrate even when the line speed is increased.

That is, the present invention is a gas barrier packaging material in which a base material layer, an adhesive layer, a gas barrier layer, an anchor coat layer, and a polyolefin resin layer are laminated in this order from the outer layer to the inner layer, The coating layer is a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, substantially containing no non-volatile aqueous agent, and having a number average particle size of 1 μm or less. The polyolefin resin layer was laminated on the anchor coat layer while performing ozone treatment on the surface of the polyolefin resin melt-extruded in contact with the anchor coat layer. The ozone treatment is performed by spraying ozone gas having a concentration of 20 to 50 L / min and 5 to 9 g / m ^3. The equipment is provided.

Moreover, this invention provides the packaging container which consists of the said gas-barrier packaging material.
Further, the present invention is a method for producing a gas barrier packaging material comprising a base material layer, a gas barrier layer and a polyolefin resin layer laminated in this order from the outer layer to the inner layer, wherein the base material layer and the gas barrier layer are combined. A step of producing a laminate by laminating via an adhesive layer, a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass in the gas barrier layer of the laminate is non-volatile A step of forming an anchor coat layer by applying and drying an aqueous dispersion having a number average particle diameter of 1 μm or less substantially free of an aqueous additive, melt extrusion of the polyolefin resin, It comprises a step of laminating the anchor coat layer while performing ozone treatment by spraying ozone gas having a concentration of 20 to 50 L / min and 5 to 9 g / m ³ on the surface in contact with the anchor coat layer. The present invention provides a method for producing a gas barrier packaging material.

According to the present invention, since a conventional AC agent can be used, it is possible to produce a gas barrier packaging material having excellent coloring resistance by using conventional equipment as it is.
Since the gas barrier packaging material of the present invention is excellent in alcohol resistance and hand cutting properties by using a predetermined AC agent, it provides a gas barrier packaging material that is excellent in long-term storage even when it contains alcohol. be able to.

  The gas barrier packaging material of the present invention adheres the gas barrier layer and the olefin resin layer via a predetermined anchor coat layer, and therefore does not use a conventional adhesive for laminating using an organic solvent, and discharges the organic solvent. The amount can be reduced, and the load on the environment can be reduced.

  According to the present invention, after a predetermined AC agent layer is formed on the gas barrier layer, it can be adjusted by adhering to the heat seal layer by extrusion lamination, and the polyolefin resin layer melt-extruded to the AC agent layer is subjected to ozone treatment. To provide an excellent method for producing a gas barrier packaging material that can improve the film feeding speed in the extrusion laminating process, and can impart coloration resistance by ozone treatment and improve production efficiency. Can do.

The present invention is a gas barrier packaging material in which a base material layer, an adhesive layer, a gas barrier layer, an anchor coat layer, and a polyolefin resin layer are laminated in this order from the outer layer to the inner layer, and the anchor coat layer of the laminate Is a polyolefin copolymer resin containing an unsaturated carboxylic acid or its anhydride in the range of 0.01 to 5% by mass, containing substantially no non-volatile aqueous additive and having a number average particle size of 1 μm or less. The polyolefin-based resin layer is formed by laminating the polyolefin-based resin layer on the surface of the melt-extruded polyolefin-based resin in contact with the anchor coat layer while performing ozone treatment. There, the ozone treatment, the concentration 20～50L / min, characterized by spraying the ozone gas 5~9g / m ^3, is a gas barrier wrapping material .

(1) Configuration of Gas Barrier Packaging Material An example of a preferred embodiment of the gas barrier packaging material of the present invention will be described with reference to the drawings.
FIG. 1 shows a substrate layer (10), an anchor coat layer (15), an adhesive layer (20), a gas barrier layer (30), an anchor coat layer (40) from the outer layer toward the inner layer, and an ozone-treated surface (53 It is sectional drawing of the gas-barrier packaging material formed by laminating | stacking the polyolefin resin layer (50) in which) was formed. An anchor coat layer (15) is laminated on the base material layer (10), an adhesive layer (20) and a gas barrier layer (30) are laminated on the anchor coat layer (15), and an anchor coat is applied on the gas barrier layer (30). The layer (40) is laminated, and then the ozone-treated surface (43) is applied to the surface of the melt-extruded polyolefin-based resin layer (50) and then laminated on the anchor coat layer (40). In addition, adhesion of the base material layer (10) and the gas barrier layer (30) can be performed, for example, by using a laminating adhesive via the adhesive layer (20), and the gas barrier packaging material thus prepared can be bonded. In some cases, the anchor coat layer (15) is not necessary.

  In addition, the present invention can ensure coloring resistance and improve laminate strength by forming an ozone-treated surface (53) on the surface of the polyolefin resin layer (50) to be laminated on a predetermined anchor coat layer (40). In view of this, there may be two or more polyolefin resin layers. This is shown in FIG. FIG. 2 shows a process for forming an ozone-coated surface (53) on the surface of a melt-extruded polyolefin-based resin (50) on an anchor coat layer (40), and then subjecting the polyolefin-based resin (50) to melt-extrusion laminating. It is sectional drawing of the gas-barrier packaging material prepared by adhere | attaching (55).

(2) Base material layer As the base material layer constituting the gas barrier packaging material of the present invention, a resin film having mechanical, physical and chemical strengths and excellent in heat resistance in the bag making process is used. Is preferred.

  Examples of the resin constituting the base material layer include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene. Copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyamide resins such as various nylons , Polyimide resin, polyamideimide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose Scan-based resin, a film made of various resins other like can be used. In particular, there are films of polypropylene resin, polyester resin, or polyamide resin.

  One or more of the above resins are used, and the resin is formed into a single layer using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. Or two or more types of resin formed into a multilayer film by co-extrusion or the like, or a mixture of two or more types of resin to form a film, and a tenter method or a tubular method, etc. Various resin films formed by stretching in the axial direction can be used.

  In the present invention, a biaxially stretched polyester film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched polyethylene naphthalate film, or a polyamide film such as nylon 6, nylon 66 or MXD-6 is biaxially stretched as a base material layer. A suitable biaxially stretched polyolefin film such as a biaxially stretched polyamide film or a biaxially stretched polypropylene can be used.

  In addition to the above, paper and synthetic paper can also be used as the base material layer. As the base material layer, any one of the above may be used alone, or two or more kinds may be used in combination.

In this invention, it is preferable that the thickness of a base material layer is 6-100 micrometers, More preferably, it is 12-16 micrometers.
(3) Adhesive layer In this invention, various adhesive layers can be used according to the adhesion method of the said base material layer and a gas barrier layer. For example, when dry laminating the base material layer and the gas barrier layer, a laminating adhesive can be used as the adhesive layer.

Laminate adhesives include two-component curable polyurethane adhesives, polyvinyl acetate adhesives, homopolymers such as ethyl acrylate, butyl, 2-ethylhexyl ester, and these, methyl methacrylate, acrylonitrile, styrene Such as polyacrylic acid ester adhesives, cyanoacrylate adhesives, and copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid. Polymer-based adhesives, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, amino resin-based adhesives such as urea resins or melamine resins, phenolic resin-based adhesives, epoxy-based adhesives, Reactive (meth) acrylic acid adhesive, chloroprene rubber Nitrile rubber, 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. 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 reaction mechanism includes a chemical reaction type, a solvent volatilization type, a heat welding type, and a hot pressure type. Either is acceptable. The amount of the laminating adhesive used 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.

  In addition, when a base material layer is a paper base material, it can also bond together by the wet lamination method. In that case, an emulsion adhesive such as an ethylene-vinyl acetate copolymer can be used as the adhesive layer.

  On the other hand, when the base material layer and the gas barrier layer are laminated by extrusion lamination, a resin that can be melt-extruded as the adhesive layer can be used as the adhesive layer. Such resins include 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, polyethylene copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer Polyolefin resins such as polymers, ethylene-propylene copolymers, methyl pentene polymers, polybutene polymers, polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid. Denatured acid change Polyolefin resins, polyvinyl acetate resins, poly (meth) acrylic resin, one or more films made of resin or sheet or coating film such as polyvinyl chloride resin and the like can be used. The thickness of the adhesive layer is 10 to 50 μm.

  In addition, when laminating | stacking a base material layer and a gas barrier layer by melt extrusion, it is preferable to apply | coat an anchor coating agent to a base material layer previously. Examples of such anchor coating agents include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents.

(4) Gas barrier layer As a gas barrier layer, the various gas-barrier base materials which can restrict | limit oxygen permeability and water vapor permeability can be used. For example, a polyvinyl alcohol film, an ethylene / vinyl alcohol copolymer, a deposited film provided with a deposited film formed by depositing an organic silicon compound, a metal or a metal oxide on a base film, and an aluminum foil can be exemplified. .

(A) Aluminum foil The aluminum foil can provide sufficient gas barrier properties with a thickness of 6 to 20 μm.
(B) Polyvinyl alcohol In this invention, polyvinyl alcohol can be used conveniently as a gas barrier layer. Although there is no restriction | limiting in the thickness of the gas barrier layer which consists of polyvinyl alcohol, Preferably it is 12-25 micrometers. Polyvinyl alcohol can be used as a single layer film, but since it is a water-soluble polymer, it may be a laminated film in which a coating film made of polyvinyl alcohol is formed on a substrate film having excellent water resistance. Such a base film can use the above-mentioned base material layer suitably. In addition, the coating film which consists of polyvinyl alcohol becomes like this. Preferably it is 0.5-3 micrometers. 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.

(C) Ethylene / vinyl alcohol copolymer In the present invention, an ethylene / vinyl alcohol copolymer can also be suitably used as the gas barrier layer. Although there is no restriction | limiting in the thickness of the gas barrier layer which consists of an ethylene vinyl alcohol copolymer, Preferably it is 12-25 micrometers. The ethylene / vinyl alcohol copolymer can be used as a single layer film, but may be a laminated film in which a coating film made of an ethylene / vinyl alcohol copolymer is formed on a base film. Such a base film can use the above-mentioned base material layer suitably. Thereby, the various characteristics according to a base film, such as a mechanical characteristic, can be improved. The coating film made of an ethylene / vinyl alcohol copolymer is preferably 0.5 to 3 μm. 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.

(D) Vapor deposition film In this invention, the vapor deposition film provided with the vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide on a base film can be used as a gas barrier layer. Such a base film can use the above-mentioned base material layer suitably. The thickness of the vapor deposition layer is suitably in the range of 150 to 2000 mm.

  The vapor deposition of the organosilicon compound, metal or metal oxide can be performed by chemical vapor deposition or physical vapor deposition. Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a base film, and an inert gas such as argon gas or helium gas is used as a carrier gas. As described above, a vapor deposition film such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

An example of a method for forming a deposited film 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.
In the present invention, the base film 201 is fed out from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film 201 is further fed at a predetermined speed via the auxiliary roll 224. Then, it is conveyed onto the circumferential surface of the cooling / electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The mixed gas composition for vapor deposition is supplied onto the substrate film 201 conveyed on the circumferential surface of the cooling / electrode drum 225, and plasma is generated and irradiated by glow discharge plasma 230 to form a vapor deposited film. . Next, when the base film 201 on which the vapor deposition film is formed as described above is wound around the winding roll 234 via the auxiliary roll 233, a vapor deposition film formed by vapor-depositing an organosilicon compound by plasma chemical vapor deposition is formed. Can do. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. 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 at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum surface to be A deposited film formed by depositing an organosilicon compound can be formed on the base film. In FIG. 3, reference numeral 235 represents a vacuum pump.

In the present invention, the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of the vapor deposition film formed by vapor-depositing the organosilicon compound obtained in this way is formed on the base film in the form of a thin film in the form of SiO _x while oxidizing the plasma-formed source gas with oxygen gas. Therefore, the deposited film is a dense continuous layer having a small gap and a high flexibility. Therefore, the barrier property of the deposited film is an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like. Compared with a deposited film of a product, it is much higher, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film is cleaned by SiO _X plasma and polar groups and free radicals are generated on the surface of the base film, the adhesion between the deposited film to be formed and the base film is high. It will be a thing. Further, the degree of vacuum at the time of forming the deposited film is 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 inorganic oxide such as silicon oxide is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, The vacuum state setting time can be shortened, the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film 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, and the reaction product is a base film. Is formed into a dense and flexible thin film, and is usually an oxidation represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a 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, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. 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 this invention, it is preferable that it is a vapor deposition film containing an organosilicate compound as said vapor deposition film. In addition to the above, the type, amount, etc. of the compound contained in the deposited film can be changed by changing the conditions of the deposition process. Under the present circumstances, as content which said compound contains in a vapor deposition film, it is 0.1 to 50%, Preferably it is 5 to 20%. If the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the vapor-deposited film will be insufficient, and scratches, cracks, etc. will easily occur due to bending, etc., and high barrier properties will be stabilized. On the other hand, it may be difficult to maintain, and if it exceeds 50%, the barrier property may be lowered.

  Furthermore, in the present invention, in the vapor deposition film obtained by vapor-depositing an organosilicon compound, it is preferable that the content of the compound decreases from the surface of the vapor deposition film in the depth direction. As a result, the impact resistance and the like are enhanced by the above-mentioned compound on the surface of the deposited film, and on the other hand, at the interface with the substrate film, the content of the above-mentioned compound is small, so that the tight adhesion between the substrate film and the deposited film is Will be strong.

  In the present invention, the deposited film is formed in the depth direction using a surface analyzer such as an X-ray photoelectron spectrometer (XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above physical properties can be confirmed by analyzing by ion etching or the like and conducting elemental analysis of the deposited film.

  In the present invention, the thickness of the deposited film is preferably about 50 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 50 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. As a means for changing the film thickness of the vapor deposition film, it can be performed by 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 or a method of slowing the vapor deposition rate. .

  In the present invention, the vapor deposition film formed by vapor-depositing an organosilicon compound, metal or metal oxide may be not only one layer of the vapor deposition film but also a multilayer film in which two or more layers are laminated and used. The materials may be used alone or as a mixture of two or more thereof, and a vapor deposition film mixed with different materials may be formed.

  In the present invention, examples of the vapor deposition monomer gas such as an organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. 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.

  On the other hand, in the present invention, a vapor deposition film formed by vapor-depositing an organosilicon compound, a metal, or a metal oxide can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an organic silicon compound by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method, A vapor deposition film formed by vapor deposition of metal or metal oxide can be formed.

  Specifically, an organic silicon compound, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a raw material is a metal or metal Using an oxidation reaction vapor deposition method in which oxygen is introduced and oxidized to be deposited on one side of the base film, and further, a plasma assisted oxidation reaction vapor deposition method in which the oxidation reaction is supported by plasma is used. A vapor deposition film can be formed. 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 of forming a vapor deposition film by physical vapor deposition will be described with reference to FIG. 4 showing a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus.

  First, the base film 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 through the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum evaporation apparatus 241. The evaporation source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 201 guided on the cooled coating drum 246, and if necessary, An oxygen gas or the like is ejected from the oxygen gas outlet 249 and a vapor deposition film formed by depositing, for example, aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. When the base film 201 on which the deposited film is formed is sent out through the guide rolls 251 and 252 and wound around the take-up roll 253, a deposited film can be formed by physical vapor deposition. First, a first-layer deposited film is formed by using the above-described winding-type vacuum deposition apparatus, and then a deposition film is further formed thereon, or the above-described winding-type vacuum deposition apparatus is connected in series. Then, the vapor deposition film may be continuously formed to form the vapor deposition film composed of two or more multilayer films.

The deposited film formed by depositing a metal or a metal oxide may basically be a thin film deposited with a metal oxide, such as silicon (Si), aluminum (Al), magnesium (Mg), Metal oxides such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) The deposited film can be used. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) 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. Generally, examples other than silicon (Si) and aluminum (Al) are poor. Therefore, 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). It is a range. In addition, although the film thickness of the said vapor deposition film changes with kinds etc. of the metal to be used or a metal oxide, it can be arbitrarily selected within the range of 50 to 2000 mm, preferably 100 to 1000 mm, for example. Moreover, the vapor deposition film formed by vapor-depositing a metal or metal oxide is used as a metal or metal oxide to be used in one kind or a mixture of two or more kinds to constitute a vapor deposition film mixed with different materials. You can also.

The vapor deposition film further 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, and M represents 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 at least one alkoxide represented by polyvinyl alcohol And a gas barrier composition obtained by polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. It is a coating film, and the composition is applied onto the vapor deposition film on the base film to provide a coating film, and it is 10 seconds to 20 ° C. to 180 ° C. and a temperature not higher than the melting point of the base film. It may be formed by heat treatment for 10 minutes. Such a gas barrier composition is described in detail in Japanese Patent Application Laid-Open No. 2008-054565.

(5) Anchor coat layer The anchor coat layer formed on the gas barrier layer in the present invention is a non-volatile aqueous auxiliary agent comprising a polyolefin copolymer resin containing unsaturated carboxylic acid or its anhydride in the range of 0.01 to 5% by mass. Can be formed by applying and drying an aqueous dispersion in which the number average particle diameter is 1 μm or less.

  The unsaturated carboxylic acid or anhydride thereof is a compound having at least one carboxyl group or acid anhydride group in the molecule, and specifically includes acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itacone. In addition to acids, itaconic anhydride, fumaric acid, crotonic acid and the like, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. The unsaturated carboxylic acid may be neutralized with a basic compound including an organic amine compound such as ammonia or triethylamine.

  The polyolefin copolymer used in the present invention is obtained by copolymerizing the unsaturated carboxylic acid or its anhydride in a polyolefin resin, and its form is not limited. For example, random copolymerization or block copolymerization is used. Any of graft copolymerization and the like may be used. The unsaturated carboxylic acid or anhydride thereof is preferably copolymerized in the range of 0.01 to 5% by mass in the polyolefin copolymer. This is because an aqueous dispersion can be prepared substantially without a non-volatile water-immobilizing aid. This non-volatile water-immobilizing auxiliary agent remains in the polyolefin copolymer resin even after the film is formed, and may plasticize the film to deteriorate the properties of the polyolefin copolymer resin, such as water resistance. In the present invention, since the non-volatile water-immobilizing aid is substantially not included, the coating properties, particularly water resistance, are excellent. “Aqueous aid” refers to a drug or compound added for the purpose of promoting aqueousization or stabilizing the aqueous dispersion in the production of an aqueous dispersion. It means that it does not have a boiling point at pressure, or has a high boiling point (for example, 300 ° C. or higher) at normal pressure. The phrase “substantially free of non-volatile aqueous solubilizer” means that the non-volatile aqueous solubilizing aid is not actively added to the system and consequently does not contain them. Such nonvolatile aqueous auxiliary agent is particularly preferably zero content, but is contained in an amount of less than 0.1% by mass with respect to the polyolefin copolymer resin component as long as the effects of the present invention are not impaired. There is no problem.

  Further, the number average particle size of the polyolefin copolymer resin is 1 μm or less, more preferably 0.5 μm or less, in view of excellent storage stability of the aqueous dispersion. Furthermore, the weight average particle diameter is also preferably 1 μm or less, and more preferably 0.5 μm or less.

  The method for obtaining the aqueous dispersion composed of the polyolefin copolymer resin is not particularly limited. For example, the polyolefin copolymer resin having the particle composition of 1 cm or less, preferably 0.8 cm or less, preferably in the form of granules or powder, The compound, water, and, if necessary, the organic solvent are heated and stirred in a container that can be sealed. As the container, a solid / liquid stirring device or an emulsifier can be used, and it is preferable to use a device capable of pressurization of 0.1 MPa or more. Aqueous dispersion can be achieved even with a simple apparatus, since sufficient aqueousity can be achieved even with low-speed stirring that allows the resin to float in an aqueous medium. Stir and mix at a temperature of 40 ° C. or lower, and then maintain the temperature in the tank at 80 to 200 ° C. and continue stirring for 5 to 120 minutes to sufficiently make the polyolefin copolymer resin aqueous and obtain an aqueous dispersion. be able to.

  In the present invention, the aqueous dispersion thus obtained is applied to the gas barrier layer so that the thickness upon drying is 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm, and then dried by heating. Form.

(6) Polyolefin-type resin layer In this invention, the polyolefin-type resin layer laminated | stacked on the said anchor coat layer comprises the heat seal layer of a packaging material, and is in contact with the said anchor-coat layer of the melt-extruded polyolefin-type resin The surface is laminated on the anchor coat layer while performing ozone treatment .

  Examples of the polyolefin resin include low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α / olefin copolymer polymerized using a single site catalyst, polypropylene, Ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Copolymers, these metal cross-linked products, methylpentene polymers, polybutene polymers, polyolefin resins such as polyethylene or polypropylene are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid Acid-modified poly Olefin resins, polyvinyl acetate resins, poly (meth) acrylic resin, polyvinyl chloride resin, may be a resin other like. Among these, those suitable for the material of the heat bonding surface of the container can be selected and used.

  In addition, when making the gas barrier packaging material easy-peeling, the polyolefin resin layer has a two-layer structure, and the surface in contact with the anchor coat layer is an ethylene-α-olefin polymerized using a single site catalyst. It is preferable to use a mixed resin layer obtained by mixing 30 to 80 parts by mass of low-density polyethylene or ethylene-based copolymer with 100 parts by mass of polybutene-1 as a copolymer layer. Thereby, easy peel property can be provided.

In the present invention, the thickness of the heat-sealable film is about 20 to 200 μm, preferably about 40 to 100 μm.
The present invention is characterized in that the melt-extruded polyolefin resin layer is subjected to ozone treatment to form an ozone-treated surface and then laminated on the anchor coat layer. Coloring resistance and laminate strength can be improved by ozone treatment of the polyolefin resin layer. In addition, the line speed can be increased by performing ozone treatment on the surface of the polyolefin resin layer that contacts the anchor coat layer.

The ozone treatment may be performed under the condition that ozone gas is sprayed at a rate of 20 to 50 L / min and 5 to 9 g / m ³ on the surface of the polyolefin resin layer that contacts the anchor coat layer. The reason why the coloration resistance is imparted by the ozone treatment is not clear, but the carboxylic acid group of the anchor coat layer reacts with the hydroxyl group of the extruded polyolefin resin oxidized by ozone, and the polyolefin copolymer resin is reticulated. This is thought to be due to a strong bond to each other.

(7) Other layers In the gas barrier packaging material of the present invention, a desired printed pattern layer can be formed between any of the layers constituting the packaging material. As the printed pattern layer, for example, a normal gravure ink composition, an offset ink composition, a relief ink composition, a screen ink composition, and other ink compositions on a base film or a gas barrier coating film. Use, for example, gravure printing method, offset printing method, letterpress printing method, silk screen printing method, and other printing methods, for example, to form a desired printing pattern consisting of characters, figures, patterns, symbols, etc. Can be configured.

  In addition, the gas barrier packaging material of the present invention improves various conditions such as anti-deformation strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality preservation, workability, hygiene, etc. Further, another layer may be laminated on any layer constituting the gas barrier packaging material.

(8) Manufacturing method of gas barrier packaging material The manufacturing method of the gas barrier packaging material of the present invention is not limited, but a step of manufacturing a laminate by laminating the base material layer and the gas barrier layer via an adhesive layer, The polyolefin copolymer resin containing unsaturated carboxylic acid or its anhydride in the range of 0.01 to 5% by mass in the gas barrier layer of the laminate is substantially free of non-volatile aqueous additive, and has a number average particle size. Applying and drying an aqueous dispersion having a diameter of 1 μm or less to form an anchor coat layer, melting and extruding the polyolefin-based resin, and performing ozone treatment on the surface in contact with the anchor coat layer, the anchor coat It can manufacture by the process laminated | stacked on a layer. In the present invention, by performing ozone treatment on the surface of the polyolefin resin layer laminated on the anchor coat layer, the line speed can be improved and coloring resistance can be imparted.

  The step of laminating the base material layer and the gas barrier layer through an adhesive layer to produce a laminate includes using an adhesive for laminating as the adhesive layer, and bonding the base material layer and the gas barrier layer with dry lamination. Alternatively, a molten resin may be used as the adhesive layer, and the base material layer and the gas barrier layer may be bonded by the melt extrusion lamination method of the adhesive layer.

  Next, the polyolefin copolymer resin containing the unsaturated carboxylic acid or the anhydride thereof in the range of 0.01 to 5% by mass in the gas barrier layer of the obtained laminate is substantially free of non-volatile aqueous additive. Then, an aqueous dispersion having a number average particle size of 1 μm or less is applied and dried. The aqueous dispersion can be applied by roll coating, gravure coating, kiss coating, or other coating methods or printing methods. The anchor coat layer has a dry thickness of 0.1 to 2 μm. In the present invention, the laminate is transferred at a line speed of 30 to 200 m / min, more preferably 100 to 160 m / min, an anchor coat layer is applied to the gas barrier layer of the laminate and dried.

Next, while maintaining the above line speed, ozone treatment is performed by spraying ozone gas having a concentration of 20 to 50 L / min and 5 to 9 g / m ^{3 on} the melt-extruded polyolefin resin layer, and the ozone-treated surface is coated with the anchor coat. Laminate into layers. Ozone treatment can produce a gas barrier packaging material that is excellent in laminate strength without lowering the line speed, and can improve productivity.

In the present invention, as described above, the gas barrier packaging material of the present invention can be produced by laminating the anchor coat layer while performing ozone treatment on the surface of the melt-extruded polyolefin-based resin in contact with the anchor coat layer. However, the polyolefin-based resin is extruded and melted, ozone-treated under the above-described conditions, and the polyolefin-based resin film is laminated while the ozone-treated surface is laminated with the anchor coat layer to produce the gas barrier packaging material of the present invention. May be. Thereby, although polyolefin-type resin is formed in two or more layers, by this, laminate strength can further be improved and hand cutting property and preservability can be improved. In addition, the extrusion temperature of the said polyolefin resin can be suitably selected according to the kind.

(9) Packaging container A packaging container can be produced using the gas barrier packaging material. For example, the polyolefin-based resin layer of the gas barrier packaging material is opposed and folded, or two of them are stacked, and the peripheral edge is heat-sealed to provide a sealing portion to form a packaging container can do. 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 form 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. Can be manufactured.

  In the above, as a heat sealing method, for example, a known method 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.

  In the present invention, the packaging container produced as described above can be suitably used for storing foods that require content resistance such as curry powder and powdered kimchi. Moreover, since it is excellent in coloring resistance even if it contains a coloring substance, it can be suitably used as a returnable packaging container by arbitrarily attaching a zipper for opening and closing.

EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
(1) Manufacture of gas-barrier packaging material An anchor coat layer was formed by applying and drying an isocyanate anchor coating agent on a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm so that the thickness when dried was 0.5 μm. . Subsequently, low density polyethylene was extruded to the anchor coat layer at an extrusion temperature of 330 ° C. to a thickness of 15 μm, and an aluminum foil having a thickness of 7 μm was bonded thereto.

  Next, an aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride (with a number average particle diameter of the dispersion resin of 0.6 μm, a non-volatile aqueous additive) is added to the aluminum foil at a line speed of 100 m / min. Use) was applied so as to have a dry thickness of 0.5 μm, and dried by heating to form an anchor coat layer.

Next, low density polyethylene was extruded to the anchor coat layer at a line speed of 100 m / min at an extrusion temperature of 330 ° C. to a thickness of 25 μm, and ozone gas was applied to the surface of the extruded layer at 30 L / min, 8.5 to 9.0 g / min. The gas barrier packaging material of the present invention was prepared by spraying with m ³ and performing ozone treatment and extrusion coating with the anchor coat layer. This is designated as a gas barrier packaging material (1).

  The layer structure of the gas barrier packaging material (1) is PET film (thickness 12 μm) / isocyanate-based AC layer (thickness 0.5 μm) / LDPE layer (thickness 15 μm) / AL foil (thickness 7 μm) / depending on the aqueous dispersion. AC layer (thickness 0.5 μm) / LDPE layer (thickness 25 μm).

(2) Evaluation of coloring resistance The gas barrier packaging material (1) is cut into a square of 100 mm length and 100 mm width, molded so as to oppose the LDPE layer, and heat-sealed on the outer periphery with a width of 10 mm. A packaging container was prepared. (I) 15 g of curry powder, (ii) 15 g of powdered kimchi, (iii) 15 g of powdered chili pepper, (iv) 20 g of a mixed solution in which ketchup, vinegar and edible oil are mixed at a mass ratio of 1: 1: 1. (V) 20 g of an 80% by volume aqueous ethanol solution was charged.

This was stored at 60 ° C. for 1 month, and the colorability was evaluated. The results are shown in Table 1.
(3) Presence / absence of delamination The gas barrier packaging material (1) is cut into a square of 100 mm length and 100 mm width, molded so as to oppose the LDPE layer, and heat-sealed at 10 mm width on the outer periphery for packaging. A container was prepared. (I) 15 g of curry powder, (ii) 15 g of powdered kimchi, (iii) 15 g of powdered chili pepper, (iv) 20 g of a mixed solution in which ketchup, vinegar and edible oil are mixed at a mass ratio of 1: 1: 1. (V) 20 g of an 80% by volume aqueous ethanol solution was charged.

This was stored at 60 ° C. for one month, and the presence or absence of peeling between the gas barrier layer and the heat seal layer was observed. The results are shown in Table 2.
(4) Measurement of laminate strength The laminate strength was measured for the packaging material that was not delaminated in (3) above. The laminate strength is obtained by cutting the gas barrier packaging material (1) to a width of 15 mm to make a test piece, and using a Tensilon measuring instrument, between the end of the test piece 15 mm and the aluminum foil and the innermost LDPE layer. The knob was peeled to form a knob, measured at a peeling rate of 50 mm / min by 90-degree peeling, and evaluated by peeling strength per 15 mm (unit: N / 15 mm). The results are shown in Tables 3 and 5.

(5) Evaluation of hand cutting properties The hand cutting properties after the storage in (3) above were evaluated by sensory evaluation, and the results are shown in Table 4. In Table 4, ◎: well cut, ○ cut, Δ not easily cut, and × not cut.

(Example 2)
The gas barrier packaging of the present invention was carried out in the same manner as in Example 1 except that instead of the aluminum foil, a vapor-deposited PET film in which aluminum oxide was vapor-deposited to a thickness of 400 mm was used on a 12 μm-thick biaxially stretched PET film. A material was prepared. This is designated as gas barrier packaging material (2).

  The layer structure of the gas barrier packaging material (2) is PET film (thickness 12 μm) / isocyanate-based AC layer (thickness 0.5 μm) / LDPE layer (thickness 15 μm) / alumina-deposited PET (thickness 12 μm) / the aqueous dispersion. AC layer (thickness 0.5 μm) / LDPE layer (thickness 25 μm).

Using the gas barrier packaging material (2), the coloring resistance, the presence or absence of delaminating, and the laminate strength were evaluated in the same manner as in Example 1. The results are shown in Tables 1-3.

(Comparative Example 1)
A gas barrier packaging material was produced in the same manner as in Example 1 except that an isocyanate anchor coating agent (trade name “A3210” manufactured by Mitsui Chemicals Polyurethanes, Inc.) was used instead of the aqueous dispersion of the polyolefin copolymer resin. did. This is designated as a comparative gas barrier packaging material (1).

  The layer structure of the comparative gas barrier packaging material (1) is PET film (thickness 12 μm) / isocyanate-based AC layer (thickness 0.5 μm) / LDPE layer (thickness 15 μm) / AL foil (thickness 7 μm) / isocyanate-based AC. Layer (thickness 0.5 μm) / LDPE layer (thickness 25 μm).

Using the gas barrier packaging material (1), the coloration resistance, presence / absence of delaminating, laminating strength, and hand tearability were evaluated in the same manner as in Example 1. The results are shown in Tables 1-4.

(Comparative Example 2)
An isocyanate anchor coating agent was applied to a 12 μm thick biaxially stretched polyethylene terephthalate film so that the thickness when dried was 0.5 μm, and dried to form an anchor coat layer. Subsequently, low density polyethylene was extruded to the anchor coat layer at an extrusion temperature of 330 ° C. to a thickness of 15 μm, and an aluminum foil having a thickness of 7 μm was bonded thereto.

  Next, an ethylene-methacrylic acid random copolymer (EMAA resin) was extruded onto the aluminum foil at an extrusion temperature of 295 ° C. to a thickness of 25 μm to produce a gas barrier packaging material. This is designated as a comparative gas barrier packaging material (2).

  The layer structure of the comparative gas barrier packaging material (2) is PET film (thickness 12 μm) / isocyanate-based AC layer (thickness 0.5 μm) / LDPE layer (thickness 15 μm) / AL foil (thickness 7 μm) / EMAA resin layer ( The thickness is 25 μm).

Using the comparative gas barrier packaging material (2), the presence / absence of delaminate, laminate strength, and hand tearability were evaluated in the same manner as in Example 1. The results are shown in Tables 2-4.

（実施例３）
ライン速度１００ｍ／分を、ライン速度１２０、１４０、１６０に代えた以外は実施例１と同様に操作してガスバリア性包装材を作製した。得られたガスバリア性包装材について、実施例１の（４）と同様に操作してラミネート強度を測定した。結果を表５に示す。

（比較例３）
オゾン処理を行わない以外は実施例３と同様に操作して、ガスバリア性包装材を作製した。得られたガスバリア性包装材について、実施例１の（４）と同様に操作してラミネート強度を測定した。結果を表５に示す。

(Example 3)
A gas barrier packaging material was produced in the same manner as in Example 1 except that the line speed of 100 m / min was changed to the line speeds of 120, 140, and 160. About the obtained gas-barrier packaging material, it operated like (4) of Example 1, and measured the laminate strength. The results are shown in Table 5.

(Comparative Example 3)
A gas barrier packaging material was produced in the same manner as in Example 3 except that ozone treatment was not performed. About the obtained gas-barrier packaging material, it operated like (4) of Example 1, and measured the laminate strength. The results are shown in Table 5.

（結果）
（１）実施例１および比較例１の結果から、アンカーコート剤として無水マレイン酸２質量％を含有するポリオレフィン共重合樹脂の水性分散液を使用し、更にアンカーコート層に積層するポリオレフィン系樹脂層にオゾン処理を行うことで、耐着色性を確保し、かつ長期に亘りラミネート強度を維持しうることが判明した。

(result)
(1) From the results of Example 1 and Comparative Example 1, a polyolefin-based resin layer that uses an aqueous dispersion of a polyolefin copolymer resin containing 2% by mass of maleic anhydride as an anchor coating agent and is further laminated on the anchor coat layer It was found that by performing the ozone treatment, the coloration resistance can be secured and the laminate strength can be maintained for a long time.

  (2) From the results of Example 1 and Example 2, this color resistance and high laminate strength are not limited to the case of using an aluminum foil as a gas barrier layer, and an aluminum oxide vapor deposition layer is laminated as a gas barrier layer. The same applies to the case, and in both the transparent gas barrier packaging material and the light-shielding gas barrier packaging material, improvement in coloring resistance and laminate strength was ensured.

  (3) From the results in Table 3, the gas barrier packaging materials of Comparative Example 1 and Comparative Example 2 had a reduced laminate strength depending on the type of contents, but the gas barrier properties of the present invention produced in Examples 1 and 2 were used. It has been found that the packaging material can maintain high laminate strength after long-term storage even when it contains highly irritating contents such as curry powder and kimchi.

  (4) From the results in Table 4, it was found that the gas barrier packaging material of the present invention produced in Example 1 was excellent in hand cutting properties even after a storage test. As shown in Table 3, this result is considered to be due to the high laminate strength of the gas barrier packaging material of the present invention.

  (5) From the results of Example 3, Comparative Example 3, and Table 5, when the line speed is 100 m / min, there is little difference in laminate strength depending on the presence or absence of ozone treatment, but as the line speed increases to 160 m / min, Laminate strength decreased in the absence of ozone treatment. This indicates that a gas barrier packaging material having a high laminate strength can be efficiently produced by the ozone treatment of the polyolefin resin layer.

  The gas barrier packaging material of the present invention is superior in content resistance, so it does not cause delamination, has excellent color resistance, can stably store contents over a long period of time, and is cut after long-term storage. Excellent properties. For this reason, it is useful for preservation of spices and the like.

FIG. 1 shows a substrate layer (10), an anchor coat layer (15), an adhesive layer (20), a gas barrier layer (30), an anchor coat layer (40) from the outer layer toward the inner layer, and an ozone-treated surface (53 Is a cross-sectional view of a gas barrier packaging material in which a polyolefin resin layer (50) is laminated. It is sectional drawing of the gas-barrier packaging material of this invention which the polyolefin resin layer of FIG. 1 consists of two layers. 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 a winding-type vacuum deposition apparatus.

Explanation of symbols

10 ... base material layer,
15 ... Anchor coat layer,
20: Adhesive layer,
30 ... barrier layer,
40: Anchor coat layer,
50 ... polyolefin resin layer,
53 ... ozone treated surface,
55 ... Polyolefin resin layer (film)

Claims (8)

A gas barrier packaging material in which a base material layer, an adhesive layer, a gas barrier layer, an anchor coat layer, and a polyolefin resin layer are laminated in this order from the outer layer to the inner layer,
The anchor coat layer of the laminate is a number average of a polyolefin copolymer resin containing an unsaturated carboxylic acid or an anhydride thereof in the range of 0.01 to 5% by mass, substantially free of non-volatile aqueous additive. An aqueous dispersion having a particle diameter of 1 μm or less is applied and dried,
The polyolefin resin layer is laminated on the anchor coat layer while performing ozone treatment on the surface of the melt-extruded polyolefin resin in contact with the anchor coat layer.
The said ozone treatment sprays ozone gas with a density | concentration of 20-50 L / min and 5-9 g / m < ³ >, The gas-barrier packaging material characterized by the above-mentioned.   The gas barrier packaging material according to claim 1, wherein the gas barrier layer is an aluminum foil or a vapor deposition film in which a vapor deposition film formed by vapor-depositing an organic silicon compound, a metal, or a metal oxide is provided on a base film. The vapor deposition film further 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, and M represents 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 at least one alkoxide represented by polyvinyl alcohol 3. A gas barrier coating film comprising a gas barrier composition comprising a resin based resin and / or an ethylene / vinyl alcohol copolymer and further obtained by polycondensation by a sol-gel method. Gas barrier packaging material. The base material layer is a biaxially stretched polyethylene terephthalate film,
The gas barrier layer is an aluminum foil;
The gas barrier packaging material according to any one of claims 1 to 3, wherein the polyolefin-based resin layer is low-density polyethylene.   The polyolefin-based resin layer is composed of an ethylene-α / olefin copolymer layer polymerized using a single-site catalyst, 30 to 80 parts by mass of low-density polyethylene or ethylene-based copolymer on 100 parts by mass of polybutene-1. The gas barrier packaging material according to any one of claims 1 to 4, wherein the gas barrier packaging material is composed of two layers including a mixed resin layer obtained by mixing the two.   The gas barrier packaging material according to any one of claims 1 to 5, which is used for packaging a coloring substance.   The packaging container which consists of a gas-barrier packaging material in any one of Claims 1-6. A method for producing a gas barrier packaging material in which a base material layer, a gas barrier layer and a polyolefin resin layer are laminated in this order from an outer layer to an inner layer,
A step of producing a laminate by laminating the base material layer and the gas barrier layer via an adhesive layer;
The polyolefin copolymer resin containing unsaturated carboxylic acid or its anhydride in the range of 0.01 to 5% by mass in the gas barrier layer of the laminate is substantially free of non-volatile aqueous additive, and has a number average particle size. Applying and drying an aqueous dispersion dispersed with a diameter of 1 μm or less to form an anchor coat layer;
From the step of melt-extruding the polyolefin-based resin, and laminating the anchor coat layer while performing ozone treatment by spraying ozone gas having a concentration of 20 to 50 L / min and 5 to 9 g / m ³ on the surface in contact with the anchor coat layer. The manufacturing method of the gas-barrier packaging material characterized by these.

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