JP4811783B2 - Composite vapor deposition film and method for producing the same - Google Patents

Description

  The present invention does not use aluminum foil, has excellent gas barrier properties, does not cause changes in the taste, quality, etc. of the contents, heat resistance, pressure resistance, heat sealability, pinhole resistance, puncture resistance, cold shock resistance In particular, the present invention relates to a composite vapor deposition film excellent in properties and printability, and further excellent in waste disposal suitability of used containers and a method for producing the same.

Retort foods that are sterilized by pressurization and heating after filling a pouch with food mainly as a content and sealing and sealing are commercially available. The packaging material for retort is required to withstand the pressure and heat sterilization, maintain the quality of the contents over a long period of time at normal temperature, and not cause taste deterioration. The conventional retort pouch has the following specifications with an aluminum foil in the intermediate layer. That is, biaxially stretched polyester film / biaxially stretched polyamide film / aluminum foil / unstretched polypropylene film, biaxially stretched polyester film / aluminum foil / biaxially stretched nylon film / unstretched polypropylene film, biaxially stretched polyester film / aluminum foil / Unstretched polypropylene film.
However, in recent years, from the viewpoint of waste disposal, retort pouches with a large proportion of aluminum foil as a material constituting pouches are classified problems and packaging materials that are easily disposed of in the classification based on the Containers and Packaging Recycling Law. Development and improvement are required.

As means for solving this problem, Patent Document 1 proposes a gas barrier film in which a layer made of a polycarboxylic acid polymer is formed on a plastic film, and a layer containing a polyvalent metal compound is arranged on the surface. is doing. However, although this film has a high barrier property against oxygen, the barrier property against water vapor is not sufficient.
On the other hand, as a film having a high barrier property for both oxygen and water vapor, a thin film layer made of aluminum oxide, silicon oxide, or a mixture thereof is formed on at least one side of a plastic film by vapor deposition, sputtering, or ion plating. This is a fact known from Patent Document 2 and the like. However, since this film has low flexibility, cracks occur in the thin film layer made of aluminum oxide, silicon oxide, or a mixture thereof due to bending or retort treatment, and the gas barrier property, particularly the barrier property against oxygen, is greatly reduced.

In order to solve this problem, it is effective to combine both. That is, the film of Patent Document 1 is supplemented with a thin film layer made of aluminum oxide, silicon oxide, or a mixture thereof used in Patent Document 2. The following two are known as specific methods.
One of them is a method of using a plastic film provided with a thin film layer deposited with aluminum oxide, silicon oxide, or a mixture thereof, as described in Patent Document 1. Thereby, the film which has barrier property with respect to oxygen and water vapor | steam can be obtained. For example, a layer structure of a retort pouch includes a plastic film (for example, a biaxially stretched polyester film) // a thin film layer deposited with aluminum oxide, silicon oxide, or a mixture thereof // a layer made of a polycarboxylic acid polymer / multivalent Lamination of a layer containing a metal compound / adhesive (essential) / reinforcing layer (eg biaxially oriented nylon film) / adhesive (essential) / polyolefin thermoplastic film sealing layer (eg, unstretched polypropylene film) Configuration (I) can be mentioned. In addition, an adhesive layer and a primer layer can be provided in each layer ("//" notation site) in order to improve the adhesion between them.

The other is that, as described in Examples 5 and 6 of Patent Document 3, a layer made of a polycarboxylic acid polymer is formed on a plastic film, and a layer containing a polyvalent metal compound is formed on the surface. In addition, the first film and the second film in which a thin film layer obtained by vapor-depositing aluminum oxide, silicon oxide, or a mixture thereof is formed on a plastic film are dry-laminated and bonded together by a known method.
For example, as a layer structure of the retort pouch, a plastic film (for example, a biaxially stretched polyester film) // a layer made of a polycarboxylic acid polymer / a layer containing a polyvalent metal compound / an adhesive layer (essential) / aluminum oxide, Thin film layer deposited with silicon oxide or a mixture thereof / adhesive (essential) / reinforcing layer (eg biaxially oriented nylon) / adhesive (essential) / sealing layer made of polyolefin thermoplastic film (eg, unstretched) (Lamination structure (II) of polypropylene film). In addition, an adhesive layer and a primer layer (E) can be provided in each layer ("//" notation site) for improving the adhesion between them.
WO03 / 091317 JP 2002-67213 A JP 2002-67237 A (Claim 1, Examples 5 and 6)

However, it has become clear that the above two methods have the following problems.
1-1. The laminated structure (I) according to Patent Document 1, that is, after forming a thin film layer obtained by vapor-depositing aluminum oxide, silicon oxide, or a mixture thereof on a plastic film, a layer made of a polycarboxylic acid polymer, In the method of forming a layer containing a valent metal compound, an adhesive layer is provided on the thin film layer as necessary, then a layer made of a polycarboxylic acid polymer, and a layer containing a polyvalent metal compound on its surface In the step of forming the film, the deposited thin film layer has low flexibility, so that cracks may occur and the target gas barrier property may not be obtained.

  1-2. In the layer structure of the pouch composed of the laminated structure (I), the arrangement of the layer composed of the polycarboxylic acid polymer and the layer containing the polyvalent metal compound is more than the thin film layer deposited with aluminum oxide, silicon oxide, or a mixture thereof, Since it is on the surface side in contact with the contents, i.e., on the seal layer side made of a polyolefin-based thermoplastic film, compared with a retort pouch made of a laminate using a conventional aluminum foil as a barrier layer, the The low molecular weight component may move from the layer containing the valent metal compound to the surface in contact with the contents, and the taste of the contents may change after retorting.

  2. In Examples 5 and 6 of Patent Document 3, the layer structure is a first film in which a layer made of a polycarboxylic acid polymer is formed on a plastic film, and a layer containing a polyvalent metal compound is formed on the surface, and a plastic film The laminated structure (II) is obtained by laminating a second film on which a thin film layer obtained by vapor-depositing aluminum oxide, silicon oxide, or a mixture thereof is bonded by a known dry laminate. The plastic film used as the base material for the first film and the second film is not particularly limited, but from the viewpoint of mechanical strength and thermal stability in order to increase the bag breaking strength during boil and retort sterilization. It is selected from among biaxially stretched nylon film, biaxially stretched polyethylene terephthalate film, and biaxially stretched polypropylene film. However, the biaxially stretched nylon film other than the biaxially stretched polyethylene terephthalate film may cause wrinkles and shrinkage due to water absorption, and the biaxially stretched polypropylene film may cause wrinkles and shrinkage due to heat. For example, when a biaxially stretched polyethylene terephthalate film is selected as the first film, the second film is a biaxially stretched nylon film or a biaxially stretched polypropylene film. When forming a layer made of a polycarboxylic acid polymer or a thin film layer deposited with aluminum oxide, silicon oxide, or a mixture thereof on the second film, the gas barrier property due to shrinkage depends on the water absorption and drying temperatures, respectively. Since there is a concern about the reduction, the humidity condition must be controlled, the drying temperature must be lowered, and the production speed must be reduced accordingly, which may reduce the production efficiency.

As a result of studies conducted by the present inventors to solve such a problem, a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound on at least one surface of the plastic film (A). It was found that such a problem can be solved by a composite vapor deposition film in which aluminum oxide, silicon oxide, or a mixture thereof is vapor-deposited on the surface of the layer (C) to form a thin film layer (D). It came to complete.
That is, in the first aspect of the present invention, a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound and a polyurethane resin are sequentially formed on at least one surface of the plastic film (A). On the surface of the layer (C) of the laminate, aluminum oxide, silicon oxide, or a mixture thereof is deposited with or without the primer layer (E) to form a thin film layer (D), Provided is a composite vapor deposition film in which a heat seal layer (G) made of a polyolefin-based thermoplastic resin is laminated on a thin film layer (D) through a reinforcing layer (F). 2nd of this invention provides the composite vapor deposition film of the said 1st invention by which the plastic film (A) was extended | stretched. 3rd of this invention provides the composite vapor deposition film of the said 1st or 2nd invention which formed the thin film layer (D) in the surface of the layer (C) through the primer layer (E). According to a fourth aspect of the present invention, the polycarboxylic acid polymer of the layer (B) comprising the polycarboxylic acid polymer is composed of at least one polymerizable monomer selected from acrylic acid, maleic acid, and methacrylic acid. A composite vapor deposition film according to any one of the first to third inventions, which is a homopolymer, a copolymer and / or a mixture thereof.

In the fifth aspect of the present invention, a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound and a polyurethane resin are sequentially applied to at least one surface of the plastic film (A). The primer layer (E) is applied to the surface of the layer (C) of the laminate, or aluminum oxide, silicon oxide, or a mixture thereof is vapor-deposited to form a thin film layer (D). The manufacturing method of the composite vapor deposition film which laminates | stacks the reinforcement layer (F) and the heat seal layer (G) which consists of a polyolefin-type thermoplastic resin in order on the surface of the said thin film layer (D) is provided.
6th of this invention provides the manufacturing method of the composite vapor deposition film of the said 5th invention by which the plastic film (A) is extended | stretched.

  A vapor deposition thin film layer (D) (hereinafter referred to as a thin film layer (D)) using the composite vapor deposition film of the present invention comprises a layer (B) comprising a polycarboxylic acid polymer and a layer containing a divalent metal compound (C ) Low molecular components contained in other layers by the thin film layer (D) when formed into a container such as a bag with a layer structure arranged at a position closer to the contents to be filled than both layers) Can be prevented from shifting to the contents, and the odor and taste of the contents such as food can be prevented from changing. In addition, the composite vapor deposition film of the present invention has a layered structure (C) of a plastic film (A), a layer (B) made of a polycarboxylic acid polymer, and a layer (C) containing a divalent metal compound. The thin film layer (D) is formed on the thin film layer (D), and a reinforcing layer (F) or a heat seal layer (G) is sequentially laminated on the thin film layer (D) as necessary. For this reason, since operation which coats a layer (B) and a layer (C) to a thin film layer (D) is not performed, generation | occurrence | production of the crack of a vapor deposition thin film layer in the manufacturing process of a film is suppressed.

The plastic film (A) constituting the composite vapor deposition film of the present invention (hereinafter sometimes abbreviated as “the film of the present invention”) is not particularly limited. For example, polyethylene terephthalate (PET), Polyester film such as polyethylene naphthalate, polyolefin film such as polyethylene or polypropylene, polystyrene film, nylon film, polyvinyl chloride film, polycarbonate film, polyacrylonitrile film, polyimide film, etc. may be used, either stretched or unstretched . If you expect more mechanical strength and thermal dimensional stability when coating and drying other layers on this film or applying thermal treatment such as evaporation, stretched film, especially A stretched film that is heat-set after stretching and made non-shrinkable is suitable. However, even a stretched film that is not heat-set can be used if it is substantially non-shrinkable.
In the plastic film (A), various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant may be used. The thickness of the plastic film (A) is not particularly limited, but a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound are laminated in order, and the layer (C ) On the surface of aluminum oxide, silicon oxide, or a mixture of these, it is practically possible considering the workability when forming a thin film layer (D), laminating other layers, and suitability for packaging. Is preferably from 3 to 200 μm, more preferably from 6 to 50 μm depending on the application, and in view of mass productivity, a continuous long film is desirable so that each layer can be formed continuously.

  As the polycarboxylic acid polymer constituting the polycarboxylic acid polymer layer (B) relating to the film of the present invention, an existing polycarboxylic acid polymer can be used, but an existing polycarboxylic acid polymer is used. Is a generic term for polymers having two or more carboxy groups in the molecule. Specifically, a homopolymer using α, β-monoethylenically unsaturated carboxylic acid as the polymerizable monomer, and only α, β-monoethylenically unsaturated carboxylic acid as the monomer component. , Copolymers of at least two of them, copolymers of α, β-monoethylenically unsaturated carboxylic acid with other ethylenically unsaturated monomers, and intramolecular such as alginic acid, carboxymethylcellulose, pectin Examples thereof include acidic polysaccharides having a carboxy group. These polycarboxylic acid polymers can be used alone or as a mixture of at least two polycarboxylic acid polymers.

  Here, typical examples of the α, β-monoethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the ethylenically unsaturated monomers copolymerizable therewith include saturated carboxylic acid vinyl esters such as ethylene, propylene and vinyl acetate, alkyl acrylates, alkyl methacrylates, alkyl itaconates, acrylonitrile, vinyl chloride, Representative examples include vinylidene chloride, vinyl fluoride, vinylidene fluoride, and styrene. When the polycarboxylic acid polymer is a copolymer of an α, β-monoethylenically unsaturated carboxylic acid and a saturated carboxylic acid vinyl ester such as vinyl acetate, further saponification may result in The ester moiety can be converted to vinyl alcohol for use.

  When the polycarboxylic acid polymer is a copolymer of an α, β-monoethylenically unsaturated carboxylic acid and another ethylenically unsaturated monomer, the gas barrier property of the resulting film, and From the viewpoint of resistance to high-temperature steam or hot water, the copolymer composition is preferably such that the α, β-monoethylenically unsaturated carboxylic acid monomer composition is 60 mol% or more. More preferably 80 mol% or more, still more preferably 90 mol% or more, and most preferably 100 mol%, that is, the polycarboxylic acid polymer is a polymer composed only of α, β-monoethylenically unsaturated carboxylic acid. It is preferable. Further, when the polycarboxylic acid polymer is a polymer composed only of α, β-monoethylenically unsaturated carboxylic acid, preferred specific examples thereof are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid. And a polymer obtained by polymerization of at least one polymerizable monomer selected from the group consisting of crotonic acid, and mixtures thereof. Preferably, a polymer, a copolymer, and / or a mixture thereof obtained by polymerization of at least one polymerizable monomer selected from acrylic acid, methacrylic acid, and maleic acid can be used. More preferably, polyacrylic acid, polymethacrylic acid, polymaleic acid, and mixtures thereof can be used. When the polycarboxylic acid polymer is an acidic polysaccharide other than the polymer of the α, β-monoethylenically unsaturated carboxylic acid monomer, for example, alginic acid can be preferably used.

The number average molecular weight of the polycarboxylic acid polymer is not particularly limited, but is preferably in the range of 2,000 to 10,000,000, and more preferably 5,000 to 1,000, from the viewpoint of film formability. , 000 is preferable.
As the polymer constituting the polycarboxylic acid polymer layer (B) according to the present invention, in addition to the polycarboxylic acid polymer, other films can be used as long as the gas barrier property of the film and the resistance to high temperature steam and hot water are not impaired. Although it is possible to use a mixture of the polymers, it is preferable to use only the polycarboxylic acid polymer alone.

In the film of the present invention, from the viewpoint of gas barrier properties of the film and stability to high-temperature steam and hot water, the polycarboxylic acid polymer used as a raw material is a dry film condition (30 ° C., The oxygen permeability coefficient measured at a relative humidity of 0% is preferably 1000 cm ³ (STP) · μm / (m ² · day · MPa) or less, more preferably 500 cm ³ (STP) · μm / (m ² · day · MPa) or less, and most preferably 100 cm ³ (STP) · μm / (m ² · day · MPa) or less.

The oxygen permeation coefficient here can be determined, for example, by the following method.
The polycarboxylic acid polymer (b) is dissolved in water to prepare a 10% by weight aqueous solution. Next, the prepared solution is coated on a plastic substrate using a bar coater and dried to prepare a coating film on which a polycarboxylic acid polymer layer having a thickness of 1 μm is formed. The oxygen permeability at 30 ° C. and 0% relative humidity when the obtained coating film is dried is measured. Here, any plastic film whose oxygen permeability is known is used as the plastic substrate. If the oxygen permeability of the resulting polycarboxylic acid polymer coating film is 1/10 or less of the oxygen permeability of the plastic film alone used as the substrate, the oxygen permeability is measured. The value can be regarded as the oxygen permeability of the polycarboxylic acid polymer layer alone.

  Plastic to improve the adhesion between the plastic film (A) and the layer (B) made of polycarboxylic acid polymer, especially to prevent delamination after heat treatment such as boil sterilization, retort sterilization, autoclave sterilization, etc. An adhesive layer can be provided between the film (A) and the layer (B) made of the polycarboxylic acid polymer. The type of adhesive is not particularly limited, but specific examples include alkyd resin, melamine resin, acrylic resin, nitrified cotton, soluble in solvents used for dry lamination, anchor coating, and primer. Examples thereof include urethane resin, polyester resin, phenol resin, amino resin, fluororesin, and epoxy resin.

  The divalent metal compound used in the layer (C) containing the divalent metal compound related to the film of the present invention is a divalent metal atom alone and its compound. Specific examples of the divalent metal include alkaline earth metals such as beryllium, magnesium and calcium, and transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc. Specific examples of the divalent metal compound include divalent metal oxides, hydroxides, carbonates, organic acid salts, inorganic acid salts, other divalent metal ammonium complexes, and divalent metal 2-4. Examples thereof include secondary amine complexes and carbonates and organic acid salts of these complexes. Organic salts include acetate, oxalate, citrate, lactate, phosphate, phosphite, hypophosphite, stearate, monoethylenically unsaturated carboxylate, etc. It is done. Examples of inorganic acid salts include chlorides, sulfates and nitrates. Other than these, there can be mentioned alkyl alkoxides of divalent metals.

  These divalent metal compounds can be used alone or as a mixture of at least two divalent metal compounds. Among them, the divalent metal compound used in the present invention is preferably an alkaline earth metal, cobalt, nickel, from the viewpoint of the gas barrier property of the film of the present invention, the resistance to high-temperature steam and hot water, and the productivity. Copper, zinc oxides, hydroxides, carbonates, cobalt, nickel, copper, zinc ammonium complexes and carbonates of the complexes can be used. Most preferably, magnesium, calcium, copper, zinc oxides, hydroxides, carbonates, and ammonium complexes of copper or zinc and carbonates of the complexes can be used.

  Moreover, in the range which does not impair the gas barrier property of the film of the present invention, and the resistance to high-temperature steam and hot water, a metal compound composed of a monovalent metal, for example, a monovalent metal salt of a polycarboxylic acid polymer is mixed, Or it can be used as contained. A preferable addition amount of the monovalent metal compound is 0.2 chemistry with respect to the carboxy group of the polycarboxylic acid polymer in terms of the gas barrier property of the film of the present invention and the resistance to high-temperature steam and hot water. It is below the equivalent. The monovalent metal compound may be partially contained in the molecule of the divalent metal salt of the polycarboxylic acid polymer.

  The form of the divalent metal compound is not particularly limited. In the film of the present invention, part or all of the divalent metal compound forms a salt with the carboxy group of the polycarboxylic acid polymer. Therefore, when a divalent metal compound that does not participate in carboxylate formation is present in the film of the present invention, the divalent metal compound is granular and has a small particle size from the viewpoint of appearance such as transparency of the film. Is preferred. Moreover, also in preparing the coating mixture for producing the film of the present invention described later, the divalent metal compound is granular and the particle size is small from the viewpoint of improving the efficiency during preparation and obtaining a more uniform coating mixture. Is preferred. The average particle size of the divalent metal compound is preferably 5 μm or less, more preferably 1 μm or less, and most preferably 0.1 μm or less.

  In the film of the present invention, the amount of the divalent metal compound relative to the amount of the polycarboxylic acid polymer in the layer (B) comprising the polycarboxylic acid polymer is the gas barrier property of the film, and the resistance to high-temperature steam and hot water. From the viewpoint, the layer (B) composed of a polycarboxylic acid polymer and the layer (C) composed of a divalent metal compound are based on the sum of the layers (B) and (C) adjacent to each other. It is preferable that the chemical equivalent ratio (ct / bt) of the total (bt) of the carboxy groups contained therein and the total (ct) of the divalent metal compound is 0.2 or more. The amount of the divalent metal compound is more preferably 0.5 chemical equivalents or more for both of the above films, in addition to the above viewpoint, from the viewpoint of film formability and transparency, 0.8 chemical equivalents or more and 10 chemicals. Equivalent or less, most preferably in the range of 1 to 5 chemical equivalents. Here, the “total carboxy group” of the adjacent layer (B) and layer (C) means the carboxy group of the polycarboxylic acid that was not involved in the reaction, and the polycarboxylic acid polymer and the divalent metal. It is used in the meaning including a carboxy group that becomes a divalent metal salt of a polycarboxylic acid produced by a reaction with a compound.

  The chemical equivalent can be determined as follows, for example. The case where the polycarboxylic acid polymer is polyacrylic acid and the divalent metal compound is magnesium oxide will be described as an example. When the weight of polyacrylic acid is 100 g, the molecular weight of the polyacrylic acid monomer unit is 72, and since there is one carboxy group per molecule of monomer, the amount of carboxy group in 100 g of polyacrylic acid. Is 1.39 mol. At this time, 1 equivalent to 100 g of polyacrylic acid is the amount of base that neutralizes 1.39 mol. Therefore, when 0.2 equivalent of magnesium oxide is mixed with 100 g of polyacrylic acid, it is sufficient to add magnesium oxide to neutralize 0.278 mol of carboxy groups. Since the valence of magnesium is divalent and the molecular weight of magnesium oxide is 40, 0.2 equivalent of magnesium oxide with respect to 100 g of polyacrylic acid is 5.6 g (0.139 mol).

  A layer comprising a polycarboxylic acid polymer (hereinafter abbreviated as “plastic film (A)”) on the surface of the plastic film (A) or the adhesive layer of the plastic film (A) provided with the adhesive layer ( B) In order to form the layer (C) containing a divalent metal compound in order, a coating method (coating method) is mainly used. The coating method (coating method) is a method of applying a coating liquid composed of a polycarboxylic acid polymer and a solvent to the plastic film (A), evaporating and drying the solvent, and then divalent metal compound and solvent on the surface. The layer (B) and the layer (C) which adjoin by applying the solution or dispersion liquid (coating liquid) which consists of these, and evaporating a solvent are the methods.

  When coating a coating liquid composed of a polycarboxylic acid polymer and a solvent on the plastic film (A), a dipping method, a spray, a coater or a printing machine is used. Coaters, types of printing machines, and coating methods: direct gravure method, reverse gravure method, kiss reverse gravure method, offset gravure method, gravure coater, reverse roll coater, micro gravure coater, air knife coater, dip coater, bar coater A comma coater, a die coater, or the like can be used.

  The method of evaporating and drying the solvent after coating a coating solution comprising a polycarboxylic acid polymer and a solvent or a dispersion on the plastic film (A) is not particularly limited. A method using natural drying, a method of drying in an oven set to a predetermined temperature, and a dryer attached to the coater, such as an arch dryer, a floating dryer, a drum dryer, and an infrared dryer can be used. The drying conditions can be arbitrarily selected as long as the plastic film (A) and the layer (B) made of the polycarboxylic acid polymer are not damaged by heat. After the layer (B) is dried, the adjacent layer (B) and layer (C) are coated by applying a solution or dispersion (coating solution) comprising a divalent metal compound and a solvent and evaporating the solvent. Form. The layer (B) made of a polycarboxylic acid polymer and the layer (C) containing a divalent metal compound need to be adjacent to each other. The total thickness of the layer (B) and the layer (C) formed on the plastic film (A) is not particularly limited, but is preferably in the range of 0.001 μm to 1 mm, more preferably The range is 01 μm to 100 μm, more preferably 0.1 μm to 10 μm.

  A coating solution comprising a polycarboxylic acid polymer and a solvent can be prepared by dissolving or dispersing the polycarboxylic acid polymer in a solvent. The solvent used here is not particularly limited as long as it can uniformly dissolve or disperse the polycarboxylic acid polymer. Specific examples of the solvent include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like. In addition to the polycarboxylic acid polymer and the solvent, other polymers, softeners, stabilizers, antiblocking agents, pressure-sensitive adhesives and montmorillonites are used as long as the gas barrier properties of the finally obtained film of the present invention are not impaired. An inorganic layered compound represented by the above can be added as appropriate. The addition amount is preferably 1% by weight or less of the content of the polycarboxylic acid polymer as the total amount of additives. In addition, a monovalent metal compound can be added to the coating liquid and used within a range that does not impair the gas barrier properties of the gas barrier laminate of the present invention finally obtained. A monovalent metal compound may be contained in the coating solution. The content of the polycarboxylic acid polymer in the coating solution composed of the polycarboxylic acid polymer and the solvent is not particularly limited, but from the viewpoint of coating suitability, it is in the range of 0.1 wt% to 50 wt%. Is preferred. Therefore, it is preferable to use a non-aqueous solvent other than water or a mixed solvent of a non-aqueous solvent and water as the solvent for the polycarboxylic acid polymer. Here, the non-aqueous solvent means a solvent other than water.

  A coating solution comprising a divalent metal compound and a solvent can be prepared by dissolving or dispersing the divalent metal compound in a solvent. The solvent used here is not particularly limited as long as it can uniformly dissolve or disperse the divalent metal compound. Specific examples of the solvent include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane , Cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate and the like can be used. As described above, the polycarboxylic polymer may easily react with the divalent metal compound in an aqueous solution to generate a non-uniform precipitate. Therefore, when a coating solution composed of a divalent metal compound and a solvent is applied onto the layer (B) composed of a polycarboxylic acid polymer, the polycarboxylic acid heavy polymer is applied at the time of coating if the solvent is water. The coalescence may react with the divalent metal compound and produce a heterogeneous precipitate. Therefore, it is preferable to use a non-aqueous solvent other than water or a mixed solvent of a non-aqueous solvent and water as the solvent for the divalent metal compound. Here, the non-aqueous solvent means a solvent other than water.

  In addition to the divalent metal compound and the solvent, the coating liquid composed of the divalent metal compound and the solvent includes a resin, a dispersant, a surfactant, a softener, a stabilizer, a film forming agent, an antiblocking agent, an adhesive, and the like. It can be added as appropriate. In particular, it is preferable to mix and use a resin soluble in the solvent system used for the purpose of improving the dispersibility of the divalent metal compound, the coatability, and the adhesion to the workpiece. Preferable examples of the resin include resins used for coating materials such as alkyd resin, melamine resin, acrylic resin, nitrified cotton, urethane resin, polyester resin, phenol resin, amino resin, fluorine resin, and epoxy resin. The composition ratio of the divalent metal compound (B) and the resin in the coating solution can be selected as appropriate, but the total amount of the divalent metal compound, resin, and other additives in the coating solution is from the viewpoint of coating suitability. It is preferably in the range of 1% to 50% by weight.

The film of the present invention is formed by depositing aluminum oxide, silicon oxide, or a mixture thereof on the surface of the divalent metal compound layer (C) with or without the primer layer (E) as described below. A thin film layer (D) is formed. The thin film layer (D) is basically a thin film obtained by making a metal oxide amorphous. These oxides include, for example, SiO _X, MO _X (In the formula, M represents a metal element, the value of X, the range is different. By metal elements) as such AlO _X is represented by The As the range of the value of X, silicon (Si) can take values in the range of 0 to 2, and aluminum (Al) in the range of 0 to 1.5. When X = 0 in the above, it is a complete metal and cannot be used except for a part. In addition, the upper limit of the range of X is a completely oxidized value. The film thickness of the thin film layer (D) on which the above-described aluminum oxide, silicon oxide, or a mixture thereof is vapor-deposited varies depending on the type of metal oxide used, for example, about 0.005 to 0.3 μm. It is more preferable that the film is arbitrarily selected and formed within a range of about 0.01 to 0.1 μm. In addition, as the thin film layer (D) used in the present invention, not only one thin film on which aluminum oxide, silicon oxide, or a mixture thereof is vapor-deposited, but also a laminate in which two or more layers are laminated, As the metal oxide to be used, a thin film of a metal oxide (inorganic oxide) which is used in one kind or a mixture of two or more kinds and mixed with different materials can also be constituted.

  The method for forming the thin film layer (D) is performed by vapor deposition. In the present invention, the vapor deposition refers to, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. It is used in the meaning including a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor deposition method and a photochemical vapor deposition method. The method of forming the thin film layer (D) by depositing aluminum oxide, silicon oxide, or a mixture thereof will be described in detail. Using the above metal / metal oxide as a raw material, this is heated to produce a plastic film (A) Vacuum deposition method that deposits on the surface, or oxidation reaction deposition method that uses metal or metal oxide as a raw material, oxidizes by introducing oxygen and deposits on the polyelter resin film, and further assists the oxidation reaction with plasma The deposited film can be formed using a plasma-assisted oxidation reaction deposition method or the like. In the present invention, when a silicon oxide vapor deposition film is formed, the vapor deposition film can be formed by plasma chemical vapor deposition using organosiloxane as a raw material.

The deposited film of silicon oxide is composed of a silicon compound having at least silicon and oxygen as constituent elements, and further contains one or more elements of carbon or hydrogen as a trace constituent element, and the film thickness is 0.01 It is preferable to be in the range of ˜0.05 μm. Thus, in the present invention, as the silicon oxide vapor deposition film as described above, a vapor deposition film formed using a plasma chemical vapor deposition method using an organic silicon compound as a raw material and utilizing a low temperature plasma generator or the like is used. can do.
Examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, and the like can be used.
Among organosilicon compounds, 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 deposited film formed. It is a raw material. Further, as the low-temperature plasma generator, for example, a generator such as high-frequency plasma, pulse wave plasma, or microwave plasma can be used. Therefore, in the present invention, in order to obtain highly active and stable plasma. For this, it is desirable to use a high-frequency plasma generator.

In addition, the adhesion between the layer (C) containing the divalent metal compound and the thin film layer (D) deposited with aluminum oxide, silicon oxide, or a mixture thereof is enhanced, and in particular, heat treatment such as boil sterilization, retort sterilization, autoclave sterilization, etc. In order to prevent subsequent delamination and the like, a primer layer (E) can be provided.
The primer agent is a polyol or an isocyanate compound, and a silane coupling agent can be added as necessary. Isocyanate compound adheres between a layer containing a divalent metal compound (C) and a thin film layer (D) deposited with aluminum oxide, silicon oxide, or a mixture thereof, by a urethane bond formed by reaction with a polyol such as acrylic polyol. It is added to increase the viscosity of the resin. It mainly acts as a cross-linking agent or a curing agent. The types are aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and aliphatic xylene diisocyanate (XDI). And monomers such as hexadiisocyanate (HMDI) and polymers and derivatives thereof can be used, and one or more of these can be used.

Further, the blending ratio of the polyol and the isocyanate compound is not particularly limited. However, if the amount of the isocyanate compound is too small, the curing may be poor, and if it is too large, blocking or the like occurs and there is a problem in processing. Therefore, the mixing ratio of the polyol and the isocyanate compound is particularly preferably when the NCO group derived from the isocyanate compound and the OH group derived from the polyol are mixed in an equivalent amount.
Furthermore, the blending ratio of the polyol and the silane coupling agent that can be added as necessary is preferably in the range of 1/1 to 1000/1 by weight, more preferably in the range of 2/1 to 100/1. That is. As a primer preparation method for forming the primer layer (E), a silane coupling agent is mixed with a polyol as necessary, a solvent and a diluent are added, and then an isocyanate compound is mixed. In addition, the primer agent includes various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenolic, sulfur-based, phosphorous, and the like. It is also possible to add antioxidants such as phyto-based agents, leveling agents, flow control agents, catalysts, crosslinking reaction accelerators, fillers, and the like. As a method for forming the primer layer (E), for example, a known coating method such as a gravure coating method or a roll coating method is used, and the primer agent is coated on the layer (C) containing the divalent metal compound, and then the coating film Can be obtained by drying, removing the solvent, and curing.

  The thickness of the primer layer (E) is not particularly limited as long as a uniform coating film can be formed, but generally it is preferably in the range of 0.001 to 2 μm. If the thickness is less than 0.001 μm, it is difficult to obtain a uniform coating film, and the adhesion may be lowered. On the other hand, when the thickness exceeds 2 μm, the coating film cannot be kept flexible because it is thick, and the coating film may be cracked due to external factors, which is not preferable. Particularly preferred is a range of 0.05 to 0.5 μm. The solvent for dissolving and diluting the primer agent for forming the primer layer (E) is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, methanol, ethanol, It is possible to use a mixture of alcohols such as isopropyl alcohol, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, etc., alone or arbitrarily. However, since an aqueous solution such as hydrochloric acid may be used to hydrolyze the silane coupling agent, it is more preferable to use a solvent in which isopropyl alcohol or the like and ethyl acetate that is a polar solvent are arbitrarily mixed as a cosolvent.

  The polyol has two or more hydroxyl groups at the polymer terminal and is reacted with an isocyanate group of an isocyanate compound added later. Among them, an acrylic polyol which is a polyol obtained by polymerizing an acrylic acid derivative monomer or a polyol obtained by copolymerizing an acrylic acid derivative monomer and other monomers is particularly preferable. As this polyol, a polyol obtained by homo- or copolymerization of an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate, or other acrylic monomer and other monomers such as styrene are copolymerized. Preferably used acrylic polyol is used.

Moreover, when the reactivity with an isocyanate compound is considered, it is preferable that the hydroxyl value of the said acrylic polyol is between 5-200 (KOHmg / g).
As an example of the silane coupling agent, a silane coupling agent containing any organic functional group can be used. For example, vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ- A silane coupling agent such as methacryloxypropylmethoxysilane or one or more hydrolysates can be used. Further, among these silane coupling agents, those having a functional group that reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing an isocyanate group such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, those containing a mercapto group such as γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, There are those containing an amino group such as n-β- (aminoethyl) -γ-aminopropyltriethoxysilane and γ-phenylaminopropyltrimethoxysilane. Furthermore, those containing an epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyl (β-methoxyethoxy) silane, etc. Such a silane coupling agent may be added with alcohol or the like and added with a hydroxyl group or the like, and one or more of these may be used.

  These silane coupling agents include a silane cup containing an organic functional group present at one end in a composite composed of a polyol and an isocyanate compound, or a functional group that reacts with a polyol hydroxyl group or an isocyanate compound isocyanate group. By providing a covalent bond by using a ring agent, a stronger primer layer 2 is formed, and a silanol group generated by hydrolysis of an alkoxy group or the like at the other end is formed by the metal in the inorganic oxide or the inorganic oxide. High adhesion with inorganic oxides can be expressed by strong interaction with a highly active hydroxyl group on the surface, and strong resistance can be obtained. Therefore, you may use what hydrolyzed the said silane coupling agent with the metal alkoxide. There is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group, etc., as long as these alkoxy groups, chloro group, acetoxy group, etc. are hydrolyzed to form a silanol group, It can be used as a primer agent for forming the primer layer (E).

  In this way, a layer (B) composed of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound are sequentially applied to at least one surface of the plastic film (A) with or without an adhesive layer. The composite vapor deposition film in which the thin film layer (D) is formed can be produced without applying the primer layer (E) to the surface of the layered product (C) or without applying the primer layer (E).

  In the film of the present invention, a reinforcing layer (F) made of a plastic material can be further provided on the thin film layer (D) in order to further increase the bag breaking strength during boil and retort sterilization. The laminating method is the same as the laminating method of the heat seal layer (G) as will be described later. The resin constituting the reinforcing layer (F) is not particularly limited in terms of mechanical strength and thermal stability, but is not limited to plastic film (A), particularly biaxially stretched nylon film, biaxial. A stretched polyethylene terephthalate film or a biaxially stretched polypropylene film is preferably used. The thickness is determined according to the material, required quality, and the like, but is generally in the range of 10 to 30 μm.

  In the film of the present invention, a heat seal layer (G) made of a polyolefin-based thermoplastic film can be provided. The heat seal layer (G) is located on the outermost side opposite to the plastic film (A) (if the plastic film (A) is the outermost layer, the heat seal layer (G) becomes the innermost layer), a thin film layer (D) or disposed adjacent to the reinforcing layer (F). Any heat seal layer (G) may be used as long as it can withstand retort processing and can be melted by heat and fused to each other. Specifically, for example, low-density polyethylene film, medium-density polyethylene film, high-density polyethylene film, linear low-density polyethylene film, polypropylene film, ethylene-vinyl acetate copolymer resin film, ionomer resin film, ethylene-acrylic acid Copolymer resin film, ethylene-ethyl acrylate copolymer resin film, ethylene-methacrylic acid copolymer film, ethylene-propylene copolymer film, methylpentene resin film, polybutene resin film, acid-modified polyolefin resin, etc. Resin films can be used. The thickness of the film is 10 to 300 μm, preferably about 20 to 100 μm.

  The heat seal layer (G) relating to the film of the present invention is particularly excellent in retort resistance and heat sealability among the heat seal films as described above, and therefore, an unstretched polypropylene resin film is used. Is preferred. In particular, for a high retort (HTST) having a temperature of 120 ° C. or higher, it is preferable to use an unstretched polypropylene resin film having a melting point of 145 to 165 ° C. Thus, among the above-mentioned unstretched polypropylene resin films having heat-sealability, the main component is an ethylene-propylene copolymer (hereinafter, all of which have propylene content), and a propylene-ethylene random copolymer. It is preferable to use a film formed from a resin such as propylene-ethylene block copolymer. If necessary, an olefin-based rubber component is added thereto, and a desired additive is optionally added, and a composition obtained by sufficiently kneading is heat-sealed by, for example, forming a film by extrusion molding or the like. It is desirable to use an unstretched polypropylene resin film.

  The method of laminating the reinforcing layer (F) and the heat seal layer (G) is a method of laminating ordinary packaging materials as described above, for example, wet lamination method, dry lamination method, solventless dry lamination method, extrusion lamination method. , T-die coextrusion molding method, coextrusion lamination method, inflation method, etc. Of these, the dry lamination method is preferred. In this invention, when performing said lamination | stacking, if necessary, pre-processings, such as a corona treatment and an ozone treatment, can be given to a film, for example.

As the adhesive used for the dry laminate, a urethane-based adhesive is preferable. Any urethane adhesive can be used as long as it is of the type used for retort. For example, a polyol component having a hydroxyl group such as polyester polyol as a two-component reactive polyurethane adhesive. And a polyisocyanate component having an isocyanate group such as diisocyanate, and those which form a urethane bond and cure by a reaction of a hydroxyl group and an isocyanate group can be used. The coating amount of the urethane adhesive is preferably about 0.5 to 5.0 g / m ² as a dry weight. Known additives such as a lubricant, an antioxidant, an antistatic agent, and a colorant can be added to the resin forming each layer of the laminate as needed, as long as the object of the present invention is not impaired. Other uses can be used as long as they are publicly known and have no sanitary problems.

The composite vapor deposition film of the present invention obtained as described above is a layered product comprising a plastic film (A), a layer (B) comprising a polycarboxylic acid polymer, and a layer (C) comprising a divalent metal compound. The basic layer structure is a thin film layer (D) formed by vapor-depositing aluminum oxide, silicon oxide, or a mixture thereof on the surface of (C), and the oxygen permeability is preferably 0.1 to 10 cm ³ (STP) / (m ² (Day · MPa) (temperature 30 ° C., relative humidity 80%), more preferably 0.1 to ⁵ cm ³ (STP) / (m ² · day · MPa). The water vapor permeability is preferably 0.1 to 10 g / (m ² · 24 h) (under conditions of 40 ° C. and relative humidity 90%), more preferably 0.1 to 5 g / (m ² · 24 h). is there. Even if the reinforcing layer (F) and the heat seal layer (G) are laminated on the composite vapor deposition film having the basic layer structure, the oxygen permeability and the water vapor permeability are not greatly affected.

  A method for making a bag using the composite vapor deposition film of the present invention will be described. For example, when the packaging container is a soft packaging bag made of a plastic film or the like, the composite vapor-deposited film produced by the method as described above is used, and the heat seal layer (G) having a surface in contact with food is opposed to the packaging container. Can be folded, or the two sheets can be overlapped, and the peripheral edge can be heat-sealed to provide a seal portion to form a bag. As the bag making method, the above composite vapor deposition film is folded with the heat seal layer (G) having a surface in contact with food facing each other, or two of them are overlapped, and further, the peripheral edge of the outer periphery thereof, For example, side seal type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, etc. Various types of packaging containers can be manufactured by heat-sealing according to the heat-sealing form. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and further, a tube container or the like can be manufactured using the composite vapor deposition film of the present invention. 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, or an ultrasonic seal can be used.

The transparent barrier retort pouch produced as described above using the composite vapor deposition film of the present invention can seal and sterilize a very wide range of foods.
Examples of foods that are particularly suitable for filling and sealing transparent barrier retort pouches include retort foods such as curry and stew, seasonings such as miso, kneaded products such as konjac, chikuwa, and koji, and smoked products such as ham and sausage Liquid or viscous foods and beverages such as cooked foods such as meatballs and hamburgers, processed fishery products, pickles, boiled rice cakes, and luxury products.

A package in which food is filled and packaged in the transparent barrier retort pouch manufactured using the composite vapor deposition film of the present invention is placed in a retort kettle, for example, at a temperature of 120 ° C. and a pressure of 2.1 kgf / cm ² · G for 30 minutes. The oxygen permeability after the retort treatment is preferably 0.1 to 10 cm ³ (STP) / (m ² · day · MPa) (temperature 30 ° C., relative humidity 80%), more preferably 0.1 to 10 cm ^3. 5 cm ³ (STP) / (m ² · day · MPa), and water vapor permeability is preferably 0.1 to 10 g / (m ² · 24 h) (under conditions of 40 ° C. and relative humidity 90%), Preferably it is 0.1-5 g / (m < ² > * 24h). Even when such a sterilization treatment is performed in a harsh manner, it has excellent barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and does not cause changes in the taste and quality of the contents. It is possible to obtain a barrier retort packaging product with excellent heat resistance, pressure resistance, heat sealability, pinhole resistance, puncture resistance, cold shock resistance, printability, and excellent container disposal after use. it can.

(Example)
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The evaluation method will be described below.
A method for producing a bag product from a sample film and a retort processing method Two composite vapor deposition films obtained in the present invention are cut into a size of 130 mm × 170 mm, and a CPP layer as a heat seal layer is arranged so as to face each other, A retort pouch was obtained by thermocompression bonding (longitudinal condition 200 ° C., 2 kg / cm ² , 0.5 seconds) with ^two vertical sides and one horizontal side having a width of 10 mm. This retort pouch was filled with 100 g of water, press sealed, and a semi-finished product was manufactured.
Next, the retort sterilization was performed in a steam retort kettle at a temperature of 120 ° C. and a pressure of 2.1 kgf / cm ² · G for 30 minutes, and the transparent barrier retort treatment package using the composite vapor deposition film of the present invention. Got.

1. Sensory test The sensory test regarding the influence of the odor component to the contents (mineral water) was done using the obtained retort processing package.
15 panelists compared the water odor of the above retorted package with the water odor of the conventional retorted package using a separately prepared aluminum foil. The table shows the number of people who evaluated that there were few.
The configuration of the conventional product is as follows, and the manufacturing method is the same as that according to the first embodiment. PET (12 μm) / AD (3.5 g / m ² ) / Al foil (9 μm) / AD (3.5 g / m ² ) / O—Ny (15 μm) / AD (3.5 g / m ² ) / CPP ( 60μm)
2. Method for Measuring Oxygen Permeability The oxygen permeability of the film was measured using an oxygen permeation tester OXTRANTM 2/20 manufactured by Modern Control under the conditions of a temperature of 30 ° C. and a relative humidity of 80%. The measuring method was based on JIS K-7126, B method (isobaric method), and ASTM D3985-81, and the measured value was expressed in unit cm ³ (STP) / (m ² · day · MPa). Here, (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
3. Method for measuring water vapor transmission rate The water vapor transmission rate of the film is measured according to method B (infrared sensor method) of the water vapor transmission test method (instrument measurement method) of JIS K-7129-1992, plastic film and sheet. Using a permeability tester PERMATRAN-W 3/31 type, measurement was performed under the conditions of 40 ° C. and 90% RH. It was expressed in units of g / (m ² · 24h). The seal layer was set on the high humidity side unless otherwise specified.

(Example 1)
Coating liquids 1, 2, 3, 4, 5 having the following constitution were prepared. The coating solution 1 is a coating solution for forming an adhesive layer for improving the adhesion between the plastic film (A) and the polycarboxylic acid polymer layer (B) (anchor coating; hereinafter AC). The coating liquid 2 is a polyacrylic acid coating liquid used as a polycarboxylic acid polymer, and the coating liquid 3 is zinc oxide for disposing a layer (C) containing a divalent metal compound formed on the surface of the layer (B). The containing resin coating liquid, the coating liquid 4 is an adhesive for dry lamination (hereinafter referred to as AD), and the coating liquid 5 is a thin film layer in which a layer (C) containing a divalent metal compound and aluminum oxide, silicon oxide, or a mixture thereof are deposited. (D) A primer layer (E) for improving the adhesion between them.
Coating liquid 1: Takei Mitsui Chemical Co., Ltd. AC agent Takelac ^TM A-525, curing agent: Takenate A-52, solvent: ethyl acetate
(Formulation) A-525 5.0kg
A-52 0.6kg
Ethyl acetate 94.4kg
Total 100kg (Non-volatile content 3wt%)
Coating liquid 2: Polyacrylic acid manufactured by Toagosei Co., Ltd .: Aron ^™ A-10H,
Solvent: water, isopropyl alcohol
(Combination) Aron ^TM A-10H (25% aqueous solution) 12 kg
Isopropyl alcohol 10kg
78 kg of water
Total 100kg (Non-volatile content 3wt%)

Coating solution 3: MgO; manufactured by Wako Pure Chemical Industries, Ltd., particle size 0.01 μm,
Polyester resin (polyester polyol); manufactured by Dainichi Seika Co., Ltd., NB-300 (non-volatile content: 17.5% by weight),
Curing agent; manufactured by Dainichi Seika Co., Ltd., Lamic B hardener (isocyanate)
(Composition) MgO 12kg
NB-300 45.7kg
Lamic B Hardener 2.3kg
Ethyl acetate 40.0kg
Total 100.0kg
(Non-volatile content 20wt%)
Coating liquid 4: Adhesive Takelac ^TM A-620, manufactured by Mitsui Takeda Chemical Co., Ltd., curing agent: Takenate A-65, solvent: ethyl acetate
(Combination) A-620 50kg
A-52 3kg
47 kg of ethyl acetate
Total 100kg (Non-volatile content 30wt%)
Coating solution 5: 20 parts by weight of acrylic polyol is weighed and mixed with 1 part by weight of γ-isocyanatopropyltrimethylsilane in a primer agent dilution solvent and stirred. Next, a mixed solution in which triidyl isocyanate (hereinafter abbreviated as TDI) as an isocyanate compound was added so that the NCO group was equivalent to the OH group of the acrylic polyol was diluted to an arbitrary concentration.

As the plastic film (A), a biaxially stretched polyethylene terephthalate film (PET: Lumirror ^TM P60 manufactured by Toray Industries, Inc., thickness 12 μm, inner corona treatment) is used. By using a color printing gravure printing machine, coating and drying sequentially, PET / AC (0.2 g / m ² ) / PAA (0.3 g / m ² ) / ZnO-containing resin (0.5 g / m as ZnO) ^A laminate comprising ² ) was obtained. The dry coating amount of each layer is shown in parentheses. Thereafter, aging is performed at 50 ° C. for 50 hours, and the polyester polyol (NB-300) in the ZnO-containing resin is reacted with an isocyanate (ramic B hardener) as a curing agent to form a ZnO-containing polyurethane resin layer. On the containing polyurethane surface, the coating liquid 5 was applied by a gravure coating method, and after drying, a primer layer (E) having a weight of 0.1 g / m ² was formed. Next, metal aluminum is evaporated on the primer layer (E) by an electron beam heating vacuum deposition apparatus, oxygen gas is introduced therein, and an aluminum oxide thin film layer (D) having a thickness of 20 × 10 ⁻³ μm is formed. Formed.

A biaxially stretched nylon film (O-Ny: Emblem ONMB ^TM manufactured by Unitika Ltd., thickness 15 μm) is formed on the surface of the thin film layer (D) on which aluminum oxide is deposited for the purpose of imparting strength to the obtained laminate. For the purpose of further imparting heat-sealing properties to the reinforcing layer (F), an unstretched polypropylene film (CPP: Allomer ^™ ET- manufactured by Showa Denko KK) is provided on the surface of the reinforcing layer (F) of the biaxially stretched nylon film. 20, a heat seal layer (G) having a thickness of 60 μm) was dry laminated. Lamination was performed using a dry laminator, and the coating liquid 4 was used as an adhesive for dry lamination (hereinafter referred to as AD). The coating amount of the adhesive is 3.5 g / m ² in a dry state. In this way, the layer structure is PET (12 μm) / AC (0.2 g / m ² ) / PAA (0.3 g / m ² ) / ZnO-containing polyurethane (0.5 g / m ² as ZnO) from the outermost layer. / Primer layer (0.1 g / m ² ) / AlOx thin film layer (0.03 g / m ² ) / AD (3.5 g / m ² ) / O—Ny (15 μm) / AD (3.5 g / m ² ) A composite vapor deposition film of / CPP (60 μm) was obtained.

(Example 2)
A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the coating liquid 3 was changed to the next coating liquid 6. In the sensory test, a composite vapor deposition film having an odor similar to or less than that of the conventional aluminum foil structure and having oxygen gas and water vapor permeability equal to or less than that of the aluminum foil structure was obtained.
Coating liquid 6: CaO; manufactured by Wako Pure Chemical Industries, Ltd.
Polyester resin (polyester polyol); manufactured by Dainichi Seika Co., Ltd., NB-300 (non-volatile content: 17.5% by weight),
Curing agent; manufactured by Dainichi Seika Co., Ltd., Lamic B hardener (isocyanate)
(Combination) CaO 12kg
NB-300 45.7kg
Lamic B Hardener 2.3kg
Ethyl acetate 40.0kg
Total 100.0kg
(Non-volatile content 20wt%)

(Example 3)
Except having changed the coating liquid 3 into the following coating liquid 7, it carried out similarly to Example 1, and obtained the composite vapor deposition film of the layer structure shown in Table 1. FIG. In the sensory test, a composite vapor deposition film having an odor less than or equal to that of the conventional aluminum foil structure and having an oxygen gas and water vapor barrier property equal to or less than that of the aluminum foil structure was obtained.
Coating liquid 7: Sumitomo Osaka Cement Co., Ltd. ultra-fine zinc oxide-containing paint ZR133, non-volatile content 33 wt% (breakdown: zinc oxide ultra-fine particles 18 wt%, other non-volatile content 15 wt%),
Curing agent: Dainippon Ink & Chemicals, Inc., isocyanate prepolymer DN980,
Solvent: Toluene and methyl ethyl ketone
(Compounding) ZR133 60kg
DN980 3kg
23kg of toluene
MEK 6kg
IPA 8kg
Total 100kg
(Non-volatile content 20wt%)

Example 4
A composite deposited film having the layer structure shown in Table 1 was obtained in the same manner as in Example 3 except that the thin film layer (D) was changed from AlOx to SiOx. In the sensory test, a composite vapor deposition film having an odor similar to or less than that of the conventional aluminum foil structure and having oxygen gas and water vapor permeability equal to or less than that of the aluminum foil structure was obtained.
(Example 5)
A composite vapor deposition film having the layer constitution shown in Table 1 was obtained in the same manner as in Example 3 except that the thin film layer (D) was changed from AlOx to a mixture of AlOx / SiOx. In the sensory test, a composite vapor deposition film having an odor similar to or less than that of the conventional aluminum foil structure and having oxygen gas and water vapor permeability equal to or less than that of the aluminum foil structure was obtained.
(Example 6)
A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 3 except that the coating liquid 5 was not applied on the ZnO-containing polyurethane surface (the primer layer (E) was not provided). It was.

(Example 7)
The plastic film (A) is changed from a biaxially stretched polyethylene film to a biaxially stretched nylon film (O-Ny: Emblem ONMB ^TM manufactured by Unitika Ltd., thickness 15 μm), and the reinforcing layer (F) is A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 3 except that the film was replaced with an axially stretched polyethylene terephthalate film (PET: Lumirror ^TM P60 manufactured by Toray Industries, Inc., thickness 12 μm, inner corona treatment). Obtained.
(Example 8)
A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the thin film layer (D) was changed from AlOx to SiOx.

Example 9
A composite deposited film having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the thin film layer (D) was changed from AlOx to a mixture of AlOx and SiOx.
(Example 10)
A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the coating liquid 5 was not applied on the ZnO-containing polyurethane surface (the primer layer (E) was not provided). It was.

(Example 11)
A composite vapor deposition film having a layer structure shown in Table 1 was obtained in the same manner as in Example 3 except that the biaxially stretched nylon film as the reinforcing layer (F) was not used.
(Example 12)
A composite vapor deposition film having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the biaxially stretched polyethylene terephthalate film as the reinforcing layer (F) was not used.

(Comparative Example 1)
A biaxially stretched polyethylene terephthalate film (A) (PET: Lumirror ^TM P60 manufactured by Toray Industries, Inc., thickness 12 μm, inner corona treatment) is provided with a primer layer (E), and then an electron beam on the primer layer (E) Metal aluminum was evaporated by a vacuum vapor deposition apparatus using a heating method, and oxygen gas was introduced therein, thereby forming an aluminum oxide thin film layer (D) having a thickness of 20 × 10 ⁻³ μm. Next, coating liquids 1, 2, and 7 were sequentially applied and dried on the thin film layer (D) in this order using a multicolor gravure printing machine, and then subjected to aging at 50 ° C. for 50 hours. Then, a reinforcing layer (F) of a biaxially stretched nylon film (O-Ny: emblem ONMB ^TM manufactured by Unitika Ltd., thickness 15 μm) was further applied on the reinforcing layer (F) to an unstretched polypropylene film (CPP : Showa Denko KK Alomar ^TM ET-20, was dry laminated in the same manner as in example 1 the heat seal layer (G) having a thickness of 60 [mu] m). Thus, PET (12 μm) / primer layer (0.1 g / m ² ) / AlOx thin film layer (0.02 g / m ² ) / AC (0.2 g / m ² ) / PAA (0.3 g / m ² ) / ZnO-containing polyurethane (0.5 g / m ² as ZnO) / AD (3.5 g / m ² ) / O—Ny (15 μm) / AD (3.5 g / m ² ) / CPP (60 μm) composite A vapor deposited film was obtained.

  The thin film layer was cracked because it passed through the gravure printing machine in the presence of the thin film layer (D) deposited with low flexibility aluminum oxide. Although there was no effect on oxygen permeability, water vapor permeability was increased. In addition, the layer (B) made of a polycarboxylic acid polymer / the layer (C) containing a divalent metal compound is in contact with the contents rather than the barrier layer made of a thin film layer (D) on which aluminum oxide is deposited. Because it is on the side, that is, the sealing layer (G) side made of a polyolefin-based thermoplastic film, compared with a retort pouch made of a laminate using a conventional aluminum foil as a barrier layer, a divalent metal is used during retorting. The low molecular weight component moved to the surface in contact with the contents from the layer (C) containing the compound, and the taste of the contents changed after retorting.

(Comparative Example 2)
A biaxially stretched polyethylene terephthalate film (PET: Lumirror ^TM P60 manufactured by Toray Industries, Inc., thickness 12 μm, inner surface corona treatment) is provided with a primer layer (E), and then the primer layer (E) is heated by an electron beam. Metallic aluminum was evaporated by a vacuum deposition apparatus, and oxygen gas was introduced therein, thereby forming an aluminum oxide thin film layer (D) having a thickness of 20 × 10 ⁻³ μm. Next, the coating liquids 7 and 2 were sequentially applied and dried on the thin film layer (D) in this order using a multicolor gravure printing machine, and then subjected to aging at 50 ° C. for 50 hours. Then, a reinforcing layer (F) of a biaxially stretched nylon film (O-Ny: emblem ONMB ^TM manufactured by Unitika Ltd., thickness 15 μm) was further applied on the reinforcing layer (F) to an unstretched polypropylene film (CPP : Showa Denko KK Alomar ^TM ET-20, was dry laminated in the same manner as in example 1 the heat seal layer (G) having a thickness of 60 [mu] m). Thus, PET (12 μm) / primer layer (0.1 g / m ² ) / AlOx thin film layer (0.02 g / m ² ) / ZnO-containing polyurethane (0.5 g / m ² as ZnO) / PAA (0.3 g / A composite vapor deposition film having a layer configuration of m ² ) / AD (3.5 g / m ² ) / O—Ny (15 μm) / AD (3.5 g / m ² ) / CPP (60 μm) was obtained.
As in Comparative Example 1, a crack occurred in the thin film layer (D), and the taste of the contents changed after retorting.

(Comparative Example 3)
A composite vapor deposition film having the layer constitution shown in Table 2 was obtained in the same manner as in Comparative Example 1 except that the biaxially stretched nylon film of the reinforcing layer (F) was not used. Cracks occurred in the thin film layer (D), and the taste of the contents changed after retorting.
(Comparative Example 4)
Except that the primer layer (E) and the aluminum oxide thin film layer (D) were not provided, a composite vapor deposition film having the layer constitution shown in Table 2 was obtained in the same manner as in Example 3.
Since there is no aluminum oxide thin film layer with water vapor barrier properties, there is no layer (aluminum oxide thin film layer) that blocks the migration of low molecular components of PAA layers and ZnO-containing polyurethane layers that have high water vapor permeability and affect the sensory test. The taste after retort treatment was changed.

(Comparative Example 5)
A composite vapor deposition film having the layer constitution shown in Table 2 was obtained in the same manner as in Comparative Example 4 except that the biaxially stretched nylon film of the reinforcing layer (F) was not used. Similar to Comparative Example 4, the water vapor permeability was high, and the taste after the retort treatment was changed.
(Comparative Example 6)
A composite vapor deposition film having the layer structure shown in Table 2 was obtained in the same manner as in Example 1 except that the coating liquids 1, 2, and 3 were not applied.
Since there was no PAA layer or ZnO-containing polyurethane layer that affected the sensory test, the sensory test had no problem. However, since only the low-flexibility aluminum oxide thin film was a barrier layer, the oxygen / water vapor permeability increased after retorting.
(Comparative Example 7)
A composite vapor deposition film having the layer structure shown in Table 2 was obtained in the same manner as in Comparative Example 6 except that the biaxially stretched nylon film as the reinforcing layer (F) was not provided.
Similar to Comparative Example 6, the oxygen / water vapor permeability increased.

Claims (6)

A layer (C) in which a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound and a polyurethane resin are sequentially formed on at least one surface of the plastic film (A). ), With or without a primer layer (E), aluminum oxide, silicon oxide, or a mixture thereof is deposited to form a thin film layer (D), and a reinforcing layer is formed on the thin film layer (D). A composite vapor deposition film, wherein a heat seal layer (G) made of a polyolefin-based thermoplastic resin is laminated via (F).   The composite vapor deposition film according to claim 1, wherein the plastic film (A) is stretched.   The composite vapor deposition film of Claim 1 or 2 which formed the thin film layer (D) in the surface of the layer (C) through the primer layer (E).   The polycarboxylic acid polymer of the layer (B) comprising the polycarboxylic acid polymer is a homopolymer or copolymer comprising at least one polymerizable monomer selected from acrylic acid, maleic acid, and methacrylic acid. The composite vapor deposition film according to any one of claims 1 to 3, which is a coalescence and / or a mixture thereof. A layer (C) in which a layer (B) made of a polycarboxylic acid polymer and a layer (C) containing a divalent metal compound and a polyurethane resin are coated in order on at least one surface of the plastic film (A). The primer layer (E) is applied to the surface of the material), or aluminum oxide, silicon oxide, or a mixture thereof is vapor-deposited to form a thin film layer (D). The manufacturing method of the composite vapor deposition film which laminates | stacks the reinforcement layer (F) and the heat-seal layer (G) which consists of a polyolefin-type thermoplastic resin in order on the surface of this. The manufacturing method of the composite vapor deposition film of Claim 5 in which the plastic film (A) is extended | stretched.