JP5151046B2 - Polyamide film laminate - Google Patents

Description

  The present invention is a film laminate having a gas barrier property using a film substrate made of a polyamide film as a base film, in particular, even before being subjected to treatment such as boiling sterilization or heating / pressure sterilization. The present invention also relates to a polyamide-based film laminate in which gas barrier properties are not lowered and delamination is less likely to occur.

  Conventionally, as packaging materials for packaging contents such as foods and pharmaceuticals that need to be subjected to boiling sterilization or heating / pressure sterilization, many of them have a laminated structure, especially a film lamination in which a gas barrier layer made of aluminum foil is laminated. The body is used a lot. However, when a film laminate in which an aluminum foil is laminated as a gas barrier layer is used, the content is not easily visible because it is opaque, and the aluminum foil remains as a lump when discarded and incinerated after use. There were bad effects such as hurting the furnace.

Therefore, as an alternative to such an aluminum-based gas barrier film laminate, an ethylene / vinyl alcohol copolymer resin film, a vinylidene chloride resin film, a vinylidene chloride resin coated film, an ethylene / vinyl alcohol copolymer resin or a metaxylylene A coextruded multilayer film or the like provided with a resin layer made of adipamide (MXD6) resin or the like in the middle is used. However, those using ethylene / vinyl alcohol copolymer resin have poor moisture resistance and have the disadvantage that the gas barrier properties are greatly reduced during boiling sterilization and heating / pressure sterilization. Those using vinylidene chloride resin are discarded. There are disadvantages that toxic gas is generated at the time of subsequent incineration and that the gas barrier property is greatly reduced during boiling sterilization, heating and pressure sterilization due to poor heat resistance. Further, the coextruded multilayer film also has a drawback that the gas barrier property is greatly lowered at high temperature and high humidity. In order to improve these problems, a film laminate in which a vapor-deposited thin film layer or a sealant of an inorganic oxide is laminated on one side of a biaxially stretched polyamide film has also been proposed (see, for example, Patent Document 1).
JP 2000-6341 A

  However, the gas barrier film laminate according to this proposal uses a biaxially stretched polyamide-based resin film made of a special resin composition, which is expensive and still insufficient in terms of gas barrier properties. Therefore, as a packaging material for long-term storage of contents that need to be subjected to boiling sterilization or heating / pressure sterilization treatment, those using a film base material made of polyester as a base film are generally used. Has been.

  The present invention has been made in the background as described above, and the object of the present invention is to provide an excellent gas barrier while using a polyamide-based film substrate that is cheaper than a polyester-based film substrate as a base film. In addition, the gas barrier property does not deteriorate even when subjected to boiling sterilization, heating / pressure sterilization, etc., and delamination is unlikely to occur even when placed in a hot and humid environment for a long time. The present invention also provides a polyamide-based film laminate that can be suitably used for packaging applications.

  (Delete)

  (Delete)

  (Delete)

In order to achieve the above-described problems, the invention according to claim 1 is characterized in that an anchor coat layer, a vapor deposition layer made of an inorganic compound, Si (OR ¹ ) _{4 is formed on} at least one surface of a film base made of a polyamide film. And R ² Si (OR ³ ) ₃ (R ¹ and R ³ are hydrolyzable groups such as CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , and R ² is an organic functional group). Alternatively, the hydrolyzate and a gas barrier coating layer, which is a heat-dried coating of a thin film composed of a gas barrier coating solution mainly composed of a water-soluble polymer having a hydroxyl group, are laminated at least in this relative order,
An easy-adhesion layer mainly composed of a urethane resin and / or a polyester resin is provided on the surface of the film base on which the vapor deposition layer made of an inorganic compound is provided,
And the said anchor coat layer consists of acrylic polyol, isocyanate, and a silane coupling agent, The polyamide-type film laminated body characterized by the above-mentioned .

Furthermore, the invention according to claim 2 is the polyamide-based film laminate according to claim 1 , wherein the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is vinyl, epoxy, methacryloxy, It has a non-aqueous functional group such as ureido and isocyanate.

Furthermore, the invention according to claim 3 is the polyamide-based film laminate according to claim 1 , wherein the organic functional group (R ² ) of the R ² Si (OR ³ ) ₃ is an isocyanate polymerized with an isocyanate group. It is a nurate.

Furthermore, the invention according to claim 4 is the polyamide-based film laminate according to claim 1 , wherein Si (OR ¹ ) ₄ is SiO ₂ and R ² Si (OR ³ ) ₃ is R ² Si (OH ) when converted to ^_3, wherein the solid content of the R 2 Si _{(OH) 3} is 1 to 50% by weight relative to the total solids content.

Furthermore, the invention according to claim 5 is the polyamide-based film laminate according to claim 1 , wherein Si (OR ¹ ) ₄ is SiO ₂ and R ² Si (OR ³ ) ₃ is R ² Si (OH ) When converted to ₃ , the compounding ratio of the solid content is in the range of SiO ₂ / (R ² Si (OH) ₃ / water-soluble polymer) = 100/100 to 100/30 by weight ratio. To do.

Furthermore, the invention according to claim 6 is the polyamide-based film laminate according to any one of claims 1 to 5 , wherein a heat seal layer is laminated on the gas barrier coating layer. .

According to the present invention, an anchor coat layer, a vapor deposition layer made of an inorganic compound, Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ , R ² is a hydrolyzable group such as CH ₃ , C ₂ H ₅ , C ₂ H ₄ OCH ₃ , R ² is an organic functional group) or a hydrolyzate thereof, Since the gas barrier coating layer formed by heating and drying the thin film of the gas barrier coating solution containing molecules as a main component is at least laminated in this relative order, it exhibits high adhesion and very high gas barrier properties. Furthermore, even if a heat-seal layer provided on the gas barrier coating layer side is used as a packaging sheet and subjected to boiling sterilization or heat / pressure sterilization treatment, the heat resistance and water resistance it had before treatment It is possible to maintain the property by the cooperation of the gas barrier coating layer and the anchor coating layer, and delamination does not occur. Moreover, even if it is stored for a long time in a high-temperature and high-humidity environment after boiling sterilization or heating / pressure sterilization treatment, the contents can be maintained for a long time even in a harsh environment. Furthermore, even if it is used as a constituent material of a packaging container having a shape or structure subject to physical stress, it is difficult to cause delamination if an easy-adhesion layer is provided on a film substrate made of a polyamide film. The range becomes very wide.

  Hereinafter, the present invention will be described in more detail with reference to the drawings.

  FIG. 1 shows a schematic cross-sectional configuration of the polyamide-based film laminate of the present invention. In this polyamide film laminate 10, an anchor coat layer 2, a vapor deposition layer 3 made of an inorganic compound, and a gas barrier coating layer 4 are laminated in this relative order on one surface of a film substrate 1 made of a polyamide film. It will be. On the other hand, FIG. 2 shows a schematic cross-sectional configuration of still another polyamide film laminate of the present invention. The polyamide-based film laminate shown in FIG. 2 has an easy-adhesion layer 18, an anchor coat layer 12, a vapor deposition layer 13 made of an inorganic compound, a gas barrier coating layer 14, on one surface of a film substrate 11 made of a polyamide film. The adhesive layer 15 and the sealant layer 16 are laminated in this relative order.

  The film bases 1 and 11 are made of a polyamide film. In a packaging material used for packaging contents subjected to boiling sterilization or heating / pressure sterilization for the purpose of long-term storage, it is common to use a film substrate made of polyester as the base film. On the other hand, the polyamide-based film laminate of the present invention uses a film substrate made of a polyamide film as described above, and can greatly reduce the cost as a packaging material, and can be obtained with a polyester substrate. Such as piercing property, impact resistance, and pinhole resistance.

  The film bases 1 and 11 are made of a nylon resin that is excellent in flexibility in a film made of a plastic material, and a stretched transparent nylon resin film is preferably used. Specifically, nylon 6 obtained by ring-opening polymerization reaction of ε-caprolactam, nylon 66 obtained by polycondensation reaction of hexamethylenediamine and adipate, and obtained by polycondensation of metaxylenediamine and adipic acid. A general-purpose film made of MXD6 nylon, nylon 11, nylon 12, or the like can be used. The stretching method may be a biaxial stretching method or a sequential stretching method. Further, the thickness is preferably in the range of about 12 to 25 μm from the viewpoints of film formability and economy. In addition, the film substrate may contain various additives and stabilizers, such as antistatic agents, ultraviolet inhibitors, plasticizers, lubricants, etc., and the surface thereof is treated with corona treatment as a pretreatment, Low-temperature plasma treatment, ion bombardment treatment, or the like may be performed, and further chemical treatment, solvent treatment, or the like may be performed.

  In addition, in order to further improve the adhesion with the anchor coat layer described later, further considering the case where it is used as a constituent member of a package having a shape or structure that is subjected to physical stress, one or both sides of this film substrate It is desirable to provide an easy adhesion layer. FIG. 2 shows an example in which an easy adhesion layer 18 is provided on the film substrate 11.

  In view of manufacturing costs, for example, the easy-adhesion layer 18 is preferably formed by applying an easy-adhesion resin at the time of polyamide film stretching. Further, considering resistance to boiling sterilization and heat / pressure sterilization treatment when used as a packaging material, it is more desirable to use a water-resistant polyurethane resin and / or an easy-adhesive mainly composed of a polyester resin. .

As an easily adhesive which has this polyurethane resin and / or a polyester resin as a main component, it may consist of a water-based polyurethane-type resin and a melamine type crosslinking agent, for example, and may consist of a polyester polyol and an isocyanate crosslinking agent.

  The anchor coat layers 2 and 12 laminated on the film substrate 1 or the easy-adhesion layer 18 on the film substrate 11 have a uniform thickness of the vapor deposition layer 3 made of an inorganic compound further laminated thereon. In this way, the initial gas barrier property is sufficiently secured, and the adhesion is dramatically improved, and the gas barrier property is lowered when boiling sterilization or heating / pressure sterilization is performed. The thin film layer is provided in order to prevent the occurrence of delamination.

  As a constituent material of the anchor coat layers 2 and 12, an organic polymer obtained by a two-component reaction between a polyol such as acrylic polyol, polyvinyl acetal, polyester polyol, and polyurethane polyol and an isocyanate compound, or a polyisocyanate compound and water Organic compounds having urea bonds, polyethyleneimine or derivatives thereof, polyolefin-based emulsions, polyimides, melamines, phenols, and organic silicas such as organically modified colloidal silica, silane coupling agents and hydrolysates thereof An anchor coat liquid mainly containing a silane compound or the like can be used. Among the main components, a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is particularly preferable.

  The anchor coat layers 2 and 12 are generally preferably provided by coating so that the thickness after drying is in the range of about 0.005 to 5 μm. More preferably, it may be in the range of about 0.01 to 1 μm. When the thickness is less than 0.005 μm, it is difficult to obtain a uniform coating film from the viewpoint of coating technology. On the other hand, when the thickness exceeds 5 μm, the effect of increasing the thickness is not expected, which is uneconomical.

  The vapor deposition layers 3 and 13 made of an inorganic compound provided on the anchor coat layers 2 and 12 having such a structure are made of oxides such as silicon, aluminum, titanium, zirconium, tin, and magnesium, nitrogen, and fluoride. It consists of a vapor-deposited thin film such as a unit or a composite thereof, and is formed by a vacuum process such as a vacuum vapor deposition method, a sputtering method, or a plasma vapor deposition method. In particular, among these constituent materials, aluminum oxide has a colorless and transparent vapor-deposited thin film, and when subjected to boiling sterilization, heating / pressure sterilization, etc., the gas barrier property, etc. that had before the treatment deteriorates. And can be used for a wide range of packaging materials.

  The appropriate thickness of the vapor deposition layers 3 and 13 varies depending on the application, but is desirably in the range of several tens to 5000 mm. If the thickness is less than 50 mm, there may be a problem in the continuity of the thin film, and if it exceeds 5000 mm, cracks are likely to occur and the flexibility is lowered. Preferably, it may be in the range of about 50 to 3000 mm.

The gas barrier coating layers 4 and 14 laminated on the vapor deposition layers 3 and 13 are Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ and R ³ are CH ₃ and C ₂ H, respectively). ₅ , a gas barrier coating mainly composed of a silicon compound represented by C ₂ H ₄ OCH ₃ or the like, R ² is an organic functional group) or a hydrolyzate thereof, and a water-soluble polymer having a hydroxyl group It is a heat-dried film of a thin film made of a solution.

  The metal alkoxide constituting part of the gas barrier coating solution is condensed after hydrolysis to form a ceramic film. However, since the metal oxide is hard and cracks easily occur due to distortion caused by volume reduction during condensation, it is very difficult to form a thin, transparent and uniform condensation film on the film. In response to such a situation, when a polymer is added to the solution, the structure can be given flexibility, and the occurrence of cracks as described above can be prevented. However, even though the solution to which the polymer is added appears to be uniformly dispersed visually, it is often microscopically separated into silicon or metal oxide of the metal alkoxide and the polymer portion, Gas barrier packaging materials tend to be barrier holes, making it difficult to obtain the desired gas barrier properties. Therefore, a polymer having a hydroxyl group is added to the solution, and a strong hydrogen bond between the hydroxyl group of the polymer and the hydrolyzate of the metal alkoxide is utilized, so that the metal oxide is well dispersed between the polymer during condensation. Thus, a high gas barrier property close to that of ceramic can be exhibited. Further, by laminating this film on a vapor deposition layer made of an inorganic compound, the gas barrier properties, water resistance, and moisture resistance are higher than the effects of each layer alone. However, a gas barrier coating layer formed by a gas barrier coating solution in which a metal alkoxide or a hydrolyzate thereof and a water-soluble polymer having a hydroxyl group are mixed is composed of hydrogen bonds, so that it swells when water acts. Easy to dissolve. Therefore, even if there is a synergistic effect due to the laminated structure with the vapor deposition layer as described above, the gas barrier property is likely to deteriorate under severe conditions such as boiling sterilization and heating / pressure sterilization treatment.

On the other hand, since the gas barrier coating layers 4 and 14 constituting a part of the present invention are made of the gas barrier coating solution having the above-described configuration, swelling can be prevented. In particular, when the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is a non-aqueous functional group such as vinyl, epoxy, methacryloxy, ureido, or isocyanate, the effect of preventing this swelling is increased. That is, since the non-aqueous functional group is hydrophobic, the water resistance is further improved.

Furthermore, when the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is an isocyanurate obtained by polymerizing an isocyanate group, the above-described effect is further increased. This ^R 2 Si ^(OR ₃₎ 3-isocyanate alkylalkoxysilane having an isocyanate group at the ^{R 2} of _3, polymerized isocyanurate body (1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate) Because it becomes. This 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate has no chemical reactivity in the isocyanurate part, but the same performance as when a chemical reaction occurs due to the polarity of the nurate part. It is known to show. Therefore, by adding 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate to Si (OR ¹ ) ₄ and a water-soluble polymer having a hydroxyl group, these are mainly based on the hydrogen bond. It is possible to prevent the gas barrier coating layers 4 and 14 made of the gas barrier coating solution as a component from swelling and improve water resistance.

In addition, while 3-isocyanatealkylalkoxysilane has high reactivity and low liquid stability, 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate has a nurate portion that is not water-soluble. It is easy to disperse in an aqueous liquid due to its polarity, the liquid viscosity can be kept stable, and its water resistance performance is equivalent to that of 3-isocyanatoalkylalkoxysilane. Furthermore, the nurate part is not only water resistant, but the water-soluble polymer having a hydroxyl group that constitutes the gas barrier coating solution with Si (OR ¹ ) ₄ depending on the polarity is unlikely to be a pore of the barrier.

  This 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate is produced by thermal condensation of 3-isocyanatealkylalkoxysilane, and may contain 3-isocyanatealkylalkoxysilane as a raw material. No problem.

  1,3,5-tris (3-trialkoxysilylpropyl) isocyanurate is more preferably used, but more preferred is 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate. The methoxy group in these constituent materials has a high hydrolysis rate, and those containing a propyl group can be obtained at a relatively low cost, which is practically advantageous.

On the other hand, when the organic functional group (R ² ) is vinyl or methacryloxy, R ² Si (OR ³ ) ₃ requires irradiation with ultraviolet rays or an electron beam in the production process, resulting in an increase in facilities and processes. Incurs high costs. Ureido groups have a specific odor, and some of those having epoxy groups may have mutagenic properties. In addition, the isocyanate group has a short pot life. For the reasons described above, isocyanurate in which isocyanate groups are polymerized is more preferable as a constituent material of the gas barrier coating solution.

Moreover, when converted into SiO ₂ for Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ for R ² Si (OH) ₃ , the solid content of R ² Si (OR ³ ) ₃ is the total solid content. It is desirable to be in the range of 1 to 50% by weight. If it is less than 1% by weight, the water resistance effect is low, and if it exceeds 50% by weight, the functional group tends to be a pore of the barrier. In consideration of water resistance required for boiling sterilization and heating / pressure sterilization and high barrier properties, it is more desirable to be in the range of 5 to 30%.

In addition, when Si (OR ¹ ) ₄ is converted to SiO ₂ and R ² Si (OR ³ ) ₃ is converted to R ² Si (OH) ₃ , the solid content is SiO ₂ / (R ² Si (OH) ₃ / water-soluble polymer) = 100/100 to 100/30, depending on film flexibility as well as water resistance and high gas barrier properties necessary for boiling sterilization and heat / pressure sterilization treatment Flexibility is sufficiently imparted and it can be suitably used as a packaging material.

Si gas barrier coating layer 4,14 ^(OR _{1) 4,} the ^{R _1,} both if _{CH 3, C 2 H 5,} C 2 H hydrolyzable group represented by 4 OCH ₃ and the like to use be able to. Among them, tetraethoxysilane is preferably used because it is relatively stable in an aqueous solvent after hydrolysis.

  On the other hand, the water-soluble polymer having a hydroxyl group is preferably polyvinyl alcohol, starch, or cellulose. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used, the gas barrier property is most excellent. This is because PVA is a polymer containing the most hydroxyl group in the monomer unit, and therefore has a very strong hydrogen bond with the hydroxyl group of the metal alkoxide after hydrolysis. PVA as used herein is generally obtained by saponifying polyvinyl acetate, and saponification is complete saponification in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain. Includes up to PVA. The molecular weight of PVA has a degree of polymerization of 300 to thousands, but any molecular weight may be used. However, in general, high molecular weight PVA having a high saponification degree and a high polymerization degree is preferably used because of high water resistance.

When tetraethoxysilane is used as Si (OR ¹ ) _{4 and} PVA is used as the water-soluble polymer as the main component of the gas barrier coating solution, a metal alkoxide or a hydrolyzate of metal alkoxide is converted into a metal oxide (for example, SiO 2). The weight ratio of the metal oxide to the water-soluble polymer when converted to ₂ ) is particularly preferably SiO ₂ / PVA of 100/10 to 100/100. If the PVA is less than 100/10, the gas barrier coating layer becomes hard, cracks are likely to occur, flexibility is lowered, and gas barrier properties are liable to deteriorate. Moreover, when PVA exceeds 100/100, it becomes easy to cause water resistance inhibition.

As a method for mixing each component of the gas barrier coating solution, for example, hydrolyzed Si (OR ¹ ) ₄ and a water-soluble polymer having a hydroxyl group, R ² Si (OR ³ ) ₃ may be mixed in any order. , Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ are separately hydrolyzed and then added to the water-soluble polymer by fine dispersion of SiO ₂ and hydrolysis efficiency of Si (OR ¹ ) ₄ Is desirable.

For the gas barrier coating solution constituting the gas barrier coating layers 4 and 14, an isocyanate compound, colloidal silica or smectite is considered in consideration of adhesion to an ink layer, an adhesive layer, etc., wettability, cracking prevention due to shrinkage, and the like. Known additives such as clay minerals, stabilizers, colorants, viscosity modifiers, and the like can be added within a range that does not impair gas barrier properties and water resistance.

  The thickness after drying is not particularly limited, but if it exceeds 50 μm, cracks are likely to occur, so it is desirable that the thickness be about 0.01 to 50 μm.

  As a method for forming the gas barrier coating layers 4 and 14, a normal coating method can be used. For example, dipping method, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spray coating, gravure offset method and the like can be employed.

  Any method can be used for drying a thin film made of a gas barrier coating solution as long as it is hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, etc. The method may be used. Further, two or more such drying methods may be combined.

  As described above, the basic structure of the polyamide-based film laminate according to the present invention has been described. However, by further providing a heat seal layer on the gas barrier coating layer side, it is provided as a more practical packaging material. May be. This heat seal layer is provided so as to be an adhesive part when forming a package such as a bag-shaped package, for example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer. , An ethylene-methacrylic acid ester copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and a resin such as a metal cross-linked product thereof.

  The thickness is determined according to the purpose of use of the packaging material, etc., but generally only needs to be in the range of about 15 to 200 μm. Further, in consideration of the shape of the package formed by such a packaging material, even if a heat seal layer is provided on the film base, the sealant is interposed via the adhesive layer 15 as shown in FIG. Even if the layer 16 is provided, it does not matter.

  The heat seal layer is a dry laminate method in which a film made of the above-mentioned resin is bonded using a two-component curable urethane adhesive, a non-solvent dry laminate method in which a non-solvent adhesive is bonded, and the above-described resin. Any of the extrusion laminating methods such as heating and melting and extruding and sticking in a curtain shape can be formed by a known laminating method.

  Moreover, a printing layer may be laminated on the gas barrier coating layers 4 and 14 as necessary, and a plurality of resin layers may be laminated via an adhesive. Furthermore, the structure which laminated | stacked the laminated sheet etc. in which the some resin layer was laminated | stacked also on the other surface of the film base material 1 via the printing layer, the heat seal layer, and also the adhesive agent may be sufficient.

  Hereinafter, the polyamide-based film laminate of the present invention will be further described with specific examples.

First, an anchor coating solution was prepared as follows.
(Preparation of anchor coating solution)
Acrylic polyol and triidyl isocyanate are added so that the amount of NCO group is equal to the OH group of the acrylic polyol, diluted with ethyl acetate so that the total solid content is 5 w%, and then β- (3,4 (Epoxycyclohexyl) trimethoxysilane was added and mixed so as to be 5 wt% based on the total solid content to obtain an anchor coating solution.

Next, the following gas barrier coating solutions (A liquid to D liquid) were prepared.
(Liquid A)
77.9 g of hydrochloric acid (0.1N) was added to 17.9 g of tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ; hereinafter referred to as TEOS) and 10 g of methanol, and the mixture was stirred for 30 minutes for hydrolysis to obtain a solid content (TEOS SiO ₂ solid content (converted value)) was 5% of the hydrolysis solution (a solution).
(Liquid B)
PVA solid content of polyvinyl alcohol 5%, water / methanol = 95/5 (weight ratio) aqueous solution.
(C liquid)
1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate is adjusted with water / IPA = 1/1 solution so that its R ² Si (OH) ₃ solid content (converted value) is 5%. To obtain a hydrolysis solution (C solution).
(Liquid D)
Hydrochloric acid (1N) is gradually added to an IPA solution of γ-glycidoxypropyltrimethoxysilane and stirred for 30 minutes for hydrolysis, followed by hydrolysis with a solution of water / IPA = 1/1. The R ² Si (OH) ₃ solid content (converted value) of the sidoxypropyltrimethoxysilane was adjusted to 5% to obtain a hydrolysis solution (liquid D).

  All the above blend ratios are solid content weight ratios.

  These gas barrier coating solutions were prepared as follows, and the blending ratios of the above-mentioned solid contents in the respective solutions were as follows to prepare gas barrier coating solutions i to e.

The solution constitution and solid content blending ratio of each gas barrier coating solution A to E are as follows.
・ Gas barrier coating solution A ... A liquid / B liquid / C liquid = 70/20/10
・ Gas barrier coating solution B ... A liquid / B liquid / D liquid = 70/20/10
・ Gas barrier coating solution C ... A liquid / B liquid / C liquid = 20/20/60
Gas barrier coating solution D ... A liquid / B liquid / C liquid = 90/5/5
・ Gas barrier coating solution E ... A liquid / B liquid = 70/30
Below, Examples 1-4 and Comparative Examples 1-2 are demonstrated in detail.

( Comparative Example 1 )
A biaxially stretched nylon film (Unitika Ltd., Emblem ON) with a thickness of 15 μm, with one side corona-treated, is used as the base film, and a thin film of anchor coat liquid i is applied to the corona-treated surface using a gravure coater. It was applied and dried, and an anchor coat layer made of a dry film having a thickness of 0.1 μm was laminated. Next, a vapor deposition layer made of aluminum oxide having a thickness of 2 nm was laminated on the anchor coat layer with a vacuum vapor deposition apparatus. Furthermore, a thin film made of the gas barrier coating solution (a) is applied on the vapor deposition layer formed in the above process again using a gravure coater, heated and dried, and a gas barrier coating layer having a thickness of 0.2 μm is laminated. The polyamide-type film laminated body which concerns on the comparative example 1 of this invention was obtained.

( Example 1 )
In the same manner as in Comparative Example 1 except that a biaxially stretched nylon film (Unitika Ltd., Emblem ONM) having a thickness of 15 μm provided with an easy-adhesion layer on one surface side as a film substrate was used. A polyamide-based film laminate according to Example 1 was prepared.

( Example 2 )
A polyamide-based film laminate according to Example 2 of the present invention was prepared in the same manner as in Example 1 except that the gas barrier coating solution B was used.

( Example 3 )
A polyamide-based film laminate according to Example 3 of the present invention was prepared in the same manner as in Example 1 except that the gas barrier coating solution C was used.

( Example 4 )
A polyamide-based film laminate according to Example 4 of the present invention was prepared in the same manner as Example 1 except that the gas barrier coating solution D was used.

( Comparative Example 2 )
A polyamide-based film laminate according to Comparative Example 2 was prepared in the same manner as in Example 1 except that the gas barrier coating solution e was used.

  Each polyamide-based film laminate obtained was evaluated for evaluation using a dry laminator, and a linear low-density polyethylene film having a thickness of 60 μm using a polyurethane-based adhesive on the gas barrier coating layer surface of each polyamide-based film laminate. A sealant made of was laminated to produce a laminate film (packaging film).

(Evaluation 1)
After making a four-sided pouch with a side of 10cm with the obtained packaging film and filling it with tap water, it was boiled (boiling) at 95 ° C for 60 minutes, and accelerated degradation of 40 ° C and 90% RH as it was Stored in room for 3 weeks. The oxygen permeability before boil treatment and after storage in the acceleration room was measured in an atmosphere at 30 ° C. and 70% relative humidity using an oxygen permeability measuring device (OXTRAN 10/50 manufactured by Modern Control). Moreover, the said packaging film was cut | disconnected by 15 mm width | variety, it was set as the small piece for a measurement, 90 degree peeling was performed using the tensilon (a tensile testing machine, the product made by Orientec), and the lamination strength was calculated | required. The measurement was performed in an atmosphere with a peeling rate of 300 mm / min and 23 ° C. and a relative humidity of 65%.

  Table 1 shows the measurement results of gas barrier properties and adhesion after boiling treatment was performed on the polyamide-based film laminate according to each example and a storage test was performed under high temperature and high humidity (40 ° C. and 90% RH). It was.

表１から明らかなように、比較例２に係るフィルム積層体は、保存試験後にガスバリア性と密着性の低下が見られるが、比較例１、実施例１〜４に係るポリアミド系フィルム積層体ではガスバリア性と密着性の劣化は見られない。比較例１のポリアミド系フィルム積層体で密着性の若干の低下が見られるが実用範囲内である。

As is clear from Table 1, the film laminate according to Comparative Example 2 shows a decrease in gas barrier properties and adhesion after the storage test, but in the polyamide film laminate according to Comparative Example 1 and Examples 1-4. There is no deterioration in gas barrier properties and adhesion. The polyamide film laminate of Comparative Example 1 shows a slight decrease in adhesion, but is within the practical range.

(Evaluation 2)
Using the packaging film, a square four-sided pouch with a side of 10 cm was prepared, and 50 g of tap water was filled therein. Each pouch was divided into two groups. One was placed in a dry state at room temperature for 24 hours, the other was immersed in water and left in a wet state for 24 hours, and then a pressure resistance test was performed on each. The pressure resistance test was performed by applying a load of 200 kgf and allowing to stand for 5 minutes. And the state of the pouch after 5 minutes passed was visually observed. The pressure resistance test was repeated 5 times, and the case where the bag was broken once or more was marked as x, and the case where the bag was not broken was marked as ◯. Table 2 shows the results of the pressure resistance test.

表２からも明らかなように、実施例１〜４に係る本発明のポリアミド系フィルム積層体ではどれも破袋はみられなかった。しかし、比較例２に係るポリアミド系フィルム積層体では、乾燥状態での破袋はみられなかったが湿潤状態では破袋した。

As is clear from Table 2, no bag breakage was observed in any of the polyamide-based film laminates of the present invention according to Examples 1 to 4 . However, in the polyamide-based film laminate according to Comparative Example 2 , no bag breakage was observed in the dry state, but the bag broke in the wet state.

It is explanatory drawing which shows the general | schematic cross-section structure of the polyamide-type film laminated body which concerns on this invention. It is explanatory drawing which shows the general | schematic cross-section structure of the other polyamide-type film laminated body which concerns on this invention.

DESCRIPTION OF SYMBOLS 1, 11 ... Film base material 2, 12 ... Anchor coat layer 3, 13 ... Deposition layer 4, 14 ... Gas barrier coating layer 15 ... Adhesive layer 16 ... Sealant layer 18 ... Easy adhesion layer

Claims (6)

On at least one surface of a film base made of a polyamide film, an anchor coat layer, a vapor deposition layer made of an inorganic compound, Si (OR ¹ ) ₄ and R ² Si (OR ³ ) ₃ (R ¹ and R ³ are CH ₃ and C _2. Gas barrier properties mainly composed of a hydrolyzable group such as H ₅ , C ₂ H ₄ OCH ₃ , a silicon compound represented by R ² is an organic functional group) or a hydrolyzate thereof, and a water-soluble polymer having a hydroxyl group A gas barrier coating layer which is a heat-dried coating of a thin film made of a coating solution is laminated at least in this relative order,
An easy-adhesion layer mainly composed of a urethane resin and / or a polyester resin is provided on the surface of the film base on which the vapor deposition layer made of an inorganic compound is provided,
And said anchor coat layer, an acrylic polyol, an isocyanate, polyamide film laminate, wherein the silane coupling agent or Ranaru. ^2. The polyamide-based film according to claim 1 , wherein the organic functional group (R ² ) of the R ² Si (OR ³ ) ₃ has a non-aqueous functional group such as vinyl, epoxy, methacryloxy, ureido, or isocyanate. Laminated body. ^2. The polyamide-based film laminate according to claim 1 , wherein the organic functional group (R ² ) of R ² Si (OR ³ ) ₃ is an isocyanurate in which an isocyanate group is polymerized. Si ^(OR _{1) 4} to _{^{SiO 2, R 2 Si (OR}} 3) 3 is ^R 2 Si _(OH) when converted to _{^{3, R 2 Si (OH)}} 3 solids are 1 to the total solid content The polyamide-based film laminate according to claim 1 , wherein the polyamide-based film laminate is 50% by weight. When Si (OR ¹ ) ₄ is converted to SiO ₂ and R ² Si (OR ³ ) ₃ is converted to R ² Si (OH) ₃ , the solid content is SiO ₂ / (R ² Si (OH) in weight ratio. ₃ / water-soluble polymer) = 100/100 to 100/30. The polyamide-based film laminate according to claim 1 , wherein   The polyamide-based film laminate according to any one of claims 1 to 5, wherein a heat seal layer is laminated on the gas barrier coating layer.

Images