JP2009202519A - Gas barrier film, packaging material, package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase adhesion of inorganic oxide layers to a substrate film made of a polyamide resin in a gas barrier film so as to suppress breaking of a film due to an elongation degradation of the whole laminated films which is caused by reduction of adhesion among films in the case where a material containing a liquid substance is packed. <P>SOLUTION: A transparent gas barrier film is composed of a structure wherein an easily adhering layer, an anchor coating layer and a metal oxide layer are set forth in this order at least on one surface of a polyamide resin substrate layer, and, in the case where a laminated film is structured by laminated sealant layers, the sealant layers are hot-melted and immersed in water and then the maximum energy value of a strength of a heat seal is set forth in a predetermined range. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a gas barrier film, a packaging material, and a packaging body, and particularly relates to a transparent gas barrier film, a transparent packaging material, and a packaging body using the transparent packaging material.

  For packaging foods, pharmaceuticals and precision electronic parts, a packaging material having excellent gas barrier properties may be used. For example, when a food is packaged with a high gas barrier packaging material, it is possible to suppress deterioration of proteins and fats and oils contained in the food, and maintain flavor and freshness over a long period of time. In addition, when a pharmaceutical product is packaged with a high gas barrier packaging material, the active ingredient can be prevented from being altered or dissipated. When an electronic component is packaged with a high gas barrier packaging material, corrosion of the metal, poor insulation, etc. Can be prevented.

  The high gas barrier packaging material has a multilayer structure including a gas barrier layer. Examples of the gas barrier layer include metal foil such as aluminum foil, polyvinylidene chloride (PVDC) layer, saponified ethylene-vinyl alcohol copolymer (EVOH) layer, and polycondensation reaction of metaxylenediamine and adipic acid. A layer made of nylon MXD6, the resulting polyamide, is used. These high gas barrier packaging materials show some relatively high gas barrier properties but have some drawbacks.

  For example, a high gas barrier packaging material containing a metal foil exhibits excellent gas barrier properties regardless of the environment such as temperature and humidity. However, the package formed using this packaging material cannot visually recognize the contents, must be treated as non-combustible material at the time of disposal, cannot use a metal detector for inspection of foreign matter after the contents are put in, etc. There are disadvantages. Moreover, the packaged product in which the contents are packaged by this package is not suitable for microwave heating.

  The high gas barrier packaging material including the PVDC layer is inexpensive and has a relatively high gas barrier property. However, this packaging material may generate harmful gases when incinerated.

  The high gas barrier packaging material including the EVOH layer or the nylon MXD6 layer has a large environmental dependency of the gas barrier property. In particular, in a high temperature and high humidity environment, the gas barrier property is remarkably deteriorated.

  In Patent Documents 1 and 2, a gas barrier film formed by forming an inorganic oxide layer made of silicon oxide, aluminum oxide, or magnesium oxide on a plastic substrate film by a vapor deposition method such as vacuum evaporation or sputtering. Is described. This gas barrier film can be formed transparent and has excellent gas barrier properties. Therefore, this gas barrier film is suitable as a high gas barrier packaging material.

  By the way, this gas barrier film is rarely used alone. Usually, this gas barrier film is laminated with another film or formed with a printing layer. For example, the gas barrier film and the heat-sealable resin layer may be laminated so that the inorganic oxide layer is interposed between the plastic base film and the heat-sealable resin layer. The present inventor has found that, for example, a packaging material employing such a structure can cause the following problems when a plastic base film made of a polyamide resin is used.

  The polyamide resin film is excellent in toughness, impact resistance, puncture resistance, bending fatigue resistance, wear resistance, and the like. Therefore, it is advantageous to use a base film made of a polyamide resin in the packaging material including the gas barrier film.

  However, the base film made of polyamide resin and the inorganic oxide layer have low adhesion, particularly when wet. Therefore, for example, when using a base film made of a polyamide resin in the previous gas barrier film, and packaging the liquid-containing contents with a packaging material containing this gas barrier film, the adhesion between the films is reduced, May cause delamination.

  Patent Document 3 describes that an anchor coat layer is interposed between a base film made of a polyamide resin and an inorganic oxide layer in order to solve this problem. When this configuration is adopted, higher adhesion can be achieved as compared with the case where the inorganic oxide layer is formed directly on the base film. However, the adhesion obtained by adopting this configuration is not always sufficient.

  On the other hand, when the liquid-containing contents are packaged with a packaging material containing a gas barrier film, the adhesion between the films is reduced, causing not only delamination, but also vibration or impact during transportation, or The package may be broken due to a drop during distribution.

  Not only the strength of the seal part (heat seal strength) but also the elongation up to the rupture greatly affects the breakage of the package. Therefore, if the seal portion extends, the impact during transportation or the like is dispersed, so that the package can be prevented from being broken. In other words, a small heat seal energy means that the seal part is difficult to stretch. In such a case, the impact cannot be dispersed and a load is locally applied to the seal part. When a heavy article is packaged with a laminated film, bag breaking tends to occur. Here, the heat seal energy indicates the resistance to stress acting on the sealing portion of the laminated film, and the heat seal strength and the elongation of the film until the film breaks when measuring the heat seal strength of the film. This means that the absorbed energy of the film until the seal portion breaks (or yields) is derived.

The base film made of polyamide resin and the inorganic oxide layer have low adhesion, particularly when wet. Therefore, particularly when the liquid-containing contents are packaged, the adhesion between the films is lowered, and it is easy to peel off from the lowered portion, so that the entire laminated film becomes difficult to stretch and breaks easily. Accordingly, it can be said that if the heat seal energy, which is an index of the easiness of elongation of the film of the packaging material, is small, the package is easily broken, and if it is large, it is difficult to occur.
U.S. Pat. No. 3,442,686 JP 49-041469 A JP 2001-81217 A

  An object of the present invention is to improve the adhesion of an inorganic oxide layer to a base film made of a polyamide resin in a gas barrier film.

According to the first aspect of the present invention, an easy-adhesion layer is provided on at least one surface of the polyamide-based resin base material layer, an anchor coat layer is provided on the easy-adhesion layer, and a film is formed on the anchor coat layer by vapor deposition. In the case of a gas barrier film having a structure provided with a coating layer made of a metal oxide, and a laminated film having a laminated structure composed of two layers obtained by laminating the surface of the coating layer of the gas barrier film and a sealant layer, The gas barrier film is characterized in that the maximum energy value of heat seal strength measured in accordance with JIS Z1707 after the sealant layer is heat-sealed and immersed in water is 0.03 to 0.5 N · m.
The invention according to claim 2 is the gas barrier film according to claim 1, wherein the easy-adhesion layer contains nitrogen atoms, adipic acid, and bisphenol glycidyl ether.
The invention according to claim 3 is characterized in that the anchor coat layer contains a reaction product of an acrylic polyol, an isocyanate compound, and a metal alkoxide or a hydrolysis product thereof. It is a film.
The invention of claim 4 is characterized in that the anchor coat layer contains at least two or more kinds of metal alkoxides, and one kind of the metal alkoxide uses an alkoxysilane having an amino group. The gas barrier film according to 1 or 2.
According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the coating layer made of the metal oxide is made of any one of aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof. It is a gas barrier film of description.
The invention according to claim 6 is characterized in that a gas barrier film made of a mixture containing a transparent resin and an inorganic substance is provided on the coating layer made of the metal oxide of the film according to claim 1. It is a film of any one of -5.
According to a seventh aspect of the present invention, the gas barrier coating is a coating comprising a metal oxide formed from a solution containing a water-soluble polymer, a tetraalkoxysilane or a hydrolysis product thereof, and a trialkoxysilane or a hydrolysis product thereof. The gas barrier film according to claim 6, wherein the gas barrier film is formed by coating on a layer and drying a coating film obtained thereby. The invention according to claim 8 is the gas barrier film according to claim 7, wherein the organic functional group other than the alkoxy group bonded to silicon of the trialkoxysilane is a hydrophobic organic functional group.
The invention according to claim 9 is a solution in which the gas barrier coating contains water, a water-soluble polymer, at least one compound selected from the group consisting of metal alkoxides, hydrolysis products thereof, and tin chloride. The gas barrier film according to claim 6, wherein the gas barrier film is formed by coating the inorganic oxide layer on the inorganic oxide layer and drying the coating film obtained thereby.
The invention of claim 10 is bonded to the gas barrier film according to any one of claims 1 to 9 and the base film with the inorganic oxide layer sandwiched between the gas barrier film and the gas barrier film. And a heat-sealing resin layer.

  The invention of claim 11 is a package comprising the transparent packaging material of claim 10.

  According to the present invention, in the gas barrier film, the adhesion of the inorganic oxide layer to the base film made of polyamide resin can be enhanced.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In each figure, the same reference numerals are given to components that exhibit the same or similar functions, and duplicate descriptions are omitted.

  FIG. 1 is a cross-sectional view schematically showing a transparent packaging material according to one embodiment of the present invention.

  The transparent packaging material 10 includes a transparent gas barrier film 11, an adhesive layer 12, and a heat sealable resin layer 13.

  The transparent gas barrier film 11 includes a base film 111, an easy adhesion layer 112, an anchor coat layer 113, a coating layer 114 made of a metal oxide, and a gas barrier film 115. Note that the term “film” and the term “sheet” may be properly used depending on the thickness, but the term “film” is used here regardless of the thickness.

  The base film 111 is a transparent film made of a polyamide resin. As the polyamide, homopolyamide, copolyamide, or a mixture thereof can be used.

  Examples of the homopolyamide include polycaprolactam (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), and polylaurin lactam (nylon). 12), polyethylenediamine adipamide (nylon 2, 6), polytetramethylene adipamide (nylon 4, 6), polyhexamethylene didipamide (nylon 6, 6), polyhexamiethylene sebacamide (nylon) 6,10), polyhexamethylene decanamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), polydecamethylene sebacamide (Nylon 10,10), polydecamethylene dodecamide (nylon 12,12) Metaxylenediamine-6 nylon (MXD6) can be used.

  Copolyamides include, for example, caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium sebacate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium seba Kate copolymers, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer can be used.

  The base film 111 may further include a material other than polyamide. For example, the base film 111 may further include a plasticizer, a low elastic modulus elastomer, lactams, or a mixture thereof.

  As the plasticizer, for example, aromatic sulfonamides, p-hydroxybenzoic acid, or esters can be used. As an elastomer having a low elastic modulus, for example, an ionomer resin, a modified polyolefin resin, a thermoplastic polyurethane, a polyether block amide, a polyester block amide, a polyether ester amide elastomer, a modified acrylic rubber, or a modified ethylene propylene rubber is used. be able to.

  Although there is no restriction | limiting in the thickness of the base film 111, the base film 111 needs to have the thickness which can achieve sufficient intensity | strength as a base material. Moreover, when the base film 111 is thick, the flexibility of the transparent packaging material 10 or the transparent gas barrier film 11 may be insufficient. The thickness of the base film 111 is, for example, in the range of 10 μm to 100 μm.

  The easy adhesion layer 112 is a transparent layer formed on one main surface of the base film 111. The easy adhesion layer 112 improves the adhesion between the inorganic oxide layer 114 and the base film 111 together with the anchor coat layer 113. And the easy-adhesion layer 112 will reduce the adhesiveness of the inorganic oxide layer 114 with respect to the base film 111, when the content containing the liquid is stored for a long time using the transparent packaging material 10 with the anchor coat layer 113. To suppress.

  The easy adhesion layer 112 contains nitrogen atoms, adipic acid, and bisphenol glycidyl ether. The nitrogen atom is derived from, for example, a urethane group and / or an amide group.

  The material of the easy adhesion layer 112 is, for example, a water-dispersible polyester polyurethane containing adipic acid as a polyester dibasic acid, a prepolymer thereof, a water-dispersible polyester polyurethane containing adipic acid as a polyester dibasic acid, or polyurea. Resin, its prepolymer, or a mixture containing two or more thereof is contained as a main component. In order to improve adhesion, a hydroxyl group, a carboxy group, or an amino group may be introduced into the main chain or terminal of these polymers.

  The material of the easy adhesion layer 112 further contains bisphenol glycidyl ether. Bisphenol glycidyl ether is a curing agent that accelerates the curing of the main component. By using bisphenol glycidyl ether, cross-linking is caused, whereby the easy-adhesion layer 112 excellent in water resistance, heat resistance, adhesiveness and film cohesiveness is obtained.

  As the bisphenol glycidyl ether, for example, a product obtained by reacting a bisphenol with epichlorohydrin and epoxidizing the molecular terminal of the reaction product can be used. Examples of bisphenols include 4,4′-dihydroxy-phenylmethane, 1,1-bis (4-hydroxy-diphenyl) -ethane, 2,2-bis (4-hydroxy-diphenyl) -ethane, 2,2 -Bis (4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -n-butane, or bis (4-hydroxyphenyl) -cyclohexyl-methane can be used. Among these, 2,2-bis (4-hydroxyphenyl) -propane generally called “bisphenol A” or 4,4′-dihydroxy-phenylmethane generally called “bisphenol F” is preferable. is there.

  The easy-adhesion layer 112 is obtained, for example, by applying a coating liquid containing the above-described components on the base film 111 and drying the coating film. In addition to this component, this coating solution may further contain an additive. As this additive, for example, an antistatic agent, a lubricant, an antifoaming agent, and a surfactant can be used. In addition, for example, a gravure roll method, a reverse gravure coat method, a roll coat method, an air knife method, and a Meyer bar coat method can be used for applying the coating liquid.

  Prior to application of the coating liquid, for example, in order to improve wettability and / or adhesion, a surface to be coated of the base film 111 may be pretreated. Examples of the pretreatment include corona discharge treatment and plasma treatment.

  When the base film 111 is stretched, the coating liquid for forming the easy-adhesion layer 112 may be applied to the stretched base film 111 or may be applied to the base film 111 during stretching. . Compared with the former method, the latter method is not only more productive and efficient than the former method, but also because the easy-adhesion layer 112 is heat-treated at a high temperature in this stretch film formation step. And it is excellent in the roll which can make the adhesive force of the base film 111 and the easily bonding layer 112 strong.

  Examples of the method for forming the easy-adhesion layer 112 during the stretch film formation step include the following methods. First, a polyamide resin film is formed as the base film 111. Subsequently, the coating liquid for forming the easily bonding layer 112 is apply | coated to the base film 111, and after preheating this, the base film 111 is used for a simultaneous biaxial stretching process with a coating film. Furthermore, the easy adhesion 112 formed on the base film 111 is obtained by performing a heat setting process.

As another method for forming the easy-adhesion layer 112 during the stretching film forming step, for example, a sequential biaxial stretching method can be exemplified. In this method, first, a polyamide resin film is formed as the substrate film 111. Next, the base film 111 is passed through heating rollers having different peripheral speeds to perform longitudinal stretching. Then, the coating liquid for forming the easily bonding layer 112 is apply | coated to the base film 111 longitudinally stretched, and after preheating this, the base film 111 is used for a horizontal stretch process with a coating film. Furthermore, the easily bonding layer 112 formed on the base film 111 is obtained by performing a heat setting process.

  The easy-adhesion layer 112 has a thickness in the range of 0.01 μm to 0.2 μm, for example. It is difficult to form the thin adhesive layer 112 as a continuous film having a uniform thickness, and it is difficult to obtain sufficient adhesion. Further, if the easy-adhesion layer 112 is made thick to some extent, the effect of improving the adhesion accompanying an increase in the film thickness is reduced. Therefore, the excessively thick easily adhesive layer 112 is not economical.

The anchor coat layer 113 is a transparent layer formed on the easy adhesion layer 112. The anchor coat layer 113 improves the adhesion between the inorganic oxide layer 114 and the base film 111 together with the easy adhesion layer 112.
In the embodiment according to claim 3, the anchor coat layer 113 includes a reaction product of a composition including a polyol and an isocyanate compound. This composition contains, for example, an acrylic polyol, an isocyanate compound, and a silane coupling agent or a hydrolysis product thereof.
In the embodiment according to claim 4, the anchor coat layer 113 contains at least two kinds of metal alkoxides, and one kind of the metal alkoxides uses an alkoxysilane having an amino group.

  Here, first, in the embodiment according to claim 3, that is, when the anchor coat layer 113 contains a reaction product of a composition containing a polyol and an isocyanate compound, for example, an acrylic polyol, an isocyanate compound and a silane coupling agent or The case where the hydrolysis product is contained is demonstrated.

  The silane coupling agent or the hydrolysis product thereof typically has an organic functional group that reacts with the hydroxyl group of the polyol and / or the isocyanate group of the isocyanate compound. Examples of such silane coupling agents include compounds having an isocyanate group such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyl. Compounds having an amino group such as trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, and γ-phenylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane And a compound having an epoxy group such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or a silane having a vinyl group such as vinyltrimethoxysilane or vinyltris (β-methoxyethoxy) silane Coupling The compound is reacted with an alcohol or the like formed by adding the hydroxyl group can be used. These compounds may be used alone or in combination.

  Among the functional groups contained in the silane coupling agent, organic functional groups other than the alkoxy group bonded to silicon react with the hydroxyl group of the polyol and / or the isocyanate group of the isocyanate compound, thereby increasing the cohesive force of the anchor coat layer 113. Further, the alkoxy group of the silane coupling agent or the silanol group generated by hydrolysis thereof is a polar group such as a hydroxyl group present on the surface of the metal or inorganic oxide contained in the coating layer 114 made of a metal oxide. A strong interaction is formed, thereby improving the adhesion between the anchor coat layer 113 and the coating layer 114 made of a metal oxide.

A silane coupling agent is typically a compound in which an alkoxy group and other organic functional groups are bonded to a silicon atom, but an alkoxy group substituted with a halogen group or an acetoxy group is used. May be. In other words, any material that generates a silanol group by hydrolysis may be used. In addition, you may use a silane coupling agent hydrolyzed with a metal alkoxide.

  The acrylic polyol is obtained by polymerizing an acrylic acid derivative monomer, or obtained by copolymerizing an acrylic acid derivative monomer and another monomer. Examples of the acrylic polyol include acrylic polyol obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, and other monomers such as this acrylic acid derivative monomer and styrene. Can be used.

  The acrylic polyol is reacted with the isocyanate group of the isocyanate compound. Considering the reactivity with the isocyanate group and the compatibility with the silane coupling agent, an acrylic polyol having a hydroxyl value in the range of 20 mgKOH / g to 350 mgKOH / g can be preferably used.

  The mixing ratio of the acrylic polyol and the silane coupling agent is, for example, in a range of 2/1 to 100/1 in mass ratio.

  Furthermore, an isocyanate compound is added in order to improve the adhesiveness with a plastic substrate or an inorganic oxide by a urethane bond formed by reacting with a polyol such as an acrylic polyol, and mainly functions as a crosslinking agent or a curing agent. Specific examples of isocyanate compounds that exhibit the above functions include aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate. Monomers such as (IPDI), one of these polymers or derivatives, or two or more thereof can be used.

  Here, the blending ratio of the acrylic polyol and the isocyanate compound is not particularly limited, but if the isocyanate compound is too small, the curing may be poor, and if it is too much, blocking or the like occurs and processing problems occur. There is. Therefore, the mixing ratio of the acrylic polyol and the isocyanate compound is preferably that the NCO group derived from the isocyanate compound is 50 times or less of the OH group derived from the acrylic polyol, and particularly preferably the NCO group and the OH group are mixed in an equivalent amount. This is the case. As a mixing method, a known method can be used and is not particularly limited.

  The anchor coat layer 113 is obtained, for example, by applying a coating liquid containing the above-described acrylic polyol, isocyanate compound, and silane coupling agent on the easy-adhesion layer 112 and drying and curing the coating film. This coating liquid can be obtained, for example, by mixing a silane coupling agent and an acrylic polyol, adding a solvent to the mixture, and further mixing with an isocyanate compound. Alternatively, it is obtained by mixing a silane coupling agent and an acrylic polyol solvent, reacting the silane coupling agent and the acrylic polyol, adding a solvent to the mixed solution, and further mixing the mixed solution and an isocyanate compound. . Alternatively, it can be obtained by adding a solvent to a mixed solution composed of only two or more kinds of silane coupling agents.

As a solvent for this coating solution, for example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, or mixtures thereof are used. can do. When an aqueous solution such as an aqueous hydrochloric acid solution is used to hydrolyze the silane coupling agent, a mixed solution of an alcohol such as isopropyl alcohol and ethyl acetate that is a polar solvent may be used as a cosolvent.

  The coating liquid can further contain an additive. Examples of the additive include tertiary amine, imidazole derivative, metal salt compound of carboxylic acid, curing accelerator such as quaternary ammonium salt and quaternary phosphonium salt, phenol-based, sulfur-based and phosphite-based antioxidants. , Leveling agents, rheology modifiers, catalysts, cross-linking accelerators, fillers, or mixtures thereof can be used.

  A general method can be used for applying the coating liquid to the easy-adhesion layer 112. For example, a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, or a gravure offset method can be used.

  Prior to application of the coating solution, for example, the surface of the easy-adhesion layer 112 may be pretreated in order to improve wettability and / or adhesion. Examples of the pretreatment include corona discharge treatment and plasma treatment.

  When the anchor coat layer 113 is thin, it is difficult to form the anchor coat layer 113 as a continuous film having a uniform thickness, and sufficient adhesion may not be obtained. The thick anchor coat layer 113 has low flexibility and may crack when the transparent gas barrier film 11 is bent or pulled. The thickness of the anchor coat layer 113 is, for example, in the range of 0.01 μm to 1 μm, and typically in the range of 0.05 μm to 0.5 μm.

Next, the embodiment according to claim 4, that is, the anchor coat layer 113 contains at least two kinds of metal alkoxides, and one kind of the metal alkoxides uses an alkoxysilane having an amino group. The case where the metal alkoxide is described is a compound represented by the general formula M (OR) _n . Here, M represents a metal such as titanium, aluminum, and zirconium or silicon, and R represents an alkyl group such as a CH ₃ group and a C ₂ H ₅ group. N represents the valence of the element M.

When alkoxysilane is used as the metal alkoxide, for example, a compound represented by the general formula Si (OR ¹ ) ₄ or R ² Si (OR ³ ) ₃ or a mixture thereof can be used as the alkoxysilane. . Here, R ¹ and R ³ represent hydrolyzable groups such as a CH ₃ group, a C ₃ H ₅ group, and a C ₂ H ₄ OCH ₃ group, and R ² represents an organic functional group.

  Examples of alkoxysilanes include vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Dimethoxysilane and the like are raised. Those containing an isocyanate group such as isocyanatepropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane, those containing a mercapto group such as γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-amino Some include amino groups such as propyltrimethoxysilane, 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, vinyltris (β-methoxyethoxy) silane A metal alkoxide such as that obtained by adding an alcohol or the like to a hydroxyl group or the like may be used, and two or more of these may be used.

  These alkoxysilanes interact with organic functional groups present at one end by mixing two or more types. Furthermore, the metal of the coating layer made of metal oxide or the surface of the coating layer made of metal oxide. By exhibiting a strong interaction with a highly polar hydroxyl group or the like, the coating layer made of a metal oxide and the base film 111 and the easy-adhesion layer 112 can exhibit high adhesion, and the desired physical properties can be obtained. is there.

  In the invention according to claim 4, since the anchor coat layer 113 contains at least two kinds of metal alkoxides, and one kind of the metal alkoxide uses an alkoxysilane containing an amino group, an amino group A metal alkoxide other than an alkoxysilane containing is a compound having a functional group capable of reacting with an amino group in the molecule. The functional group is an epoxy group, a carboxyl group, an isocyanate group, an oxazolinyl group or the like.

Specific examples of the compound having a functional group capable of reacting with the amino group in the molecule include phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycerol diglycidyl ether, trimethylolpropane diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hydroquinone diglycidyl ether, Bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, Glycidyl ethers such as Taerythritol tetraglycidyl ether; Glycidyl esters such as adipic acid diglycidyl ester and phthalic acid diglycidyl ester; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4 Epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Methyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysila , .Gamma.-glycidoxypropyl methyl epoxy group diethoxy silane and Si (OR ⁴⁾ group (R ⁴ is a hydrogen atom, a lower alkyl group or an acyl group) a silane coupling agent having a (hereinafter epoxy group-containing silane coupling May be abbreviated as ring agent); isocyanate groups such as γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane, γ-isocyanopropylmethyldiethoxysilane And Si (OR ⁴ ) group-containing silane coupling agent (hereinafter sometimes referred to as isocyanate group-containing silane coupling agent); tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane Triisocyanate, Isocyanates such as tolidine diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate can be used, and one or more of these can be used. Further, the compound may be a polymer organic compound having a functional group capable of reacting with an amino group, or a polymer organic compound further having a Si (OR ⁴ ) group.

Examples of the solvent for the coating liquid include esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, water, or a mixture thereof. Can be used.

  The coating liquid can further contain an additive. Examples of the additive include tertiary amine, imidazole derivative, metal salt compound of carboxylic acid, curing accelerator such as quaternary ammonium salt and quaternary phosphonium salt, phenol-based, sulfur-based and phosphite-based antioxidants. , Leveling agents, rheology modifiers, catalysts, cross-linking accelerators, fillers, or mixtures thereof can be used.

  A general method can be used for applying the coating liquid to the easy-adhesion layer 112. For example, a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, or a gravure offset method can be used.

  Prior to application of the coating solution, for example, the surface of the easy-adhesion layer 112 may be pretreated in order to improve wettability and / or adhesion. Examples of the pretreatment include corona discharge treatment and plasma treatment.

  When the anchor coat layer 113 is thin, it is difficult to form the anchor coat layer 113 as a continuous film having a uniform thickness, and sufficient adhesion may not be obtained. The thick anchor coat layer 113 has low flexibility and may crack when the transparent gas barrier film 11 is bent or pulled. The thickness of the anchor coat layer 113 is, for example, in the range of 0.01 μm to 1 μm, and typically in the range of 0.05 μm to 0.5 μm.

  The coating layer 114 made of a metal oxide is made of a vapor-deposited film of a metal oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency and gas barrier properties such as oxygen and water vapor. What is necessary is just to have. Among them, aluminum oxide and silicon oxide are particularly preferable. However, the coating layer 114 made of the metal oxide of the present invention is not limited to the metal oxide described above, and any material that meets the above conditions can be used.

  The optimum thickness of the coating layer 114 made of a metal oxide varies depending on the type and configuration of the inorganic compound used, but is generally in the range of 5 to 300 nm, and the value is appropriately selected. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. If the film thickness exceeds 300 nm, the coating layer made of the metal oxide cannot maintain flexibility, and the coating layer made of the metal oxide is cracked due to external factors such as bending and pulling after the film formation. May occur. Preferably, it exists in the range of 10-150 nm.

  Various means can be used for forming the coating layer 114 made of a metal oxide on the anchor coat layer 113, but it is generally formed by a vacuum deposition method. Sputtering, ion plating, plasma vapor deposition (CVD), or the like can be used as means other than this vacuum vapor deposition. However, considering productivity, the vacuum deposition method is the best at present. Any one of an electron beam heating method, a resistance heating method, and an induction heating method may be appropriately used as a heating means of the vacuum evaporation apparatus by this vacuum evaporation method. In order to improve the adhesion between the coating layer made of metal oxide and the plastic substrate and the denseness of the coating layer made of metal oxide, a plasma assist method or an ion beam assist method can be used. Further, in order to increase the transparency of the coating layer made of a metal oxide, it is possible to carry out reactive vapor deposition by blowing oxygen gas or the like at the time of vapor deposition.

Examples of the material for forming the gas barrier coating 115 include a water-soluble polymer and at least one metal alkoxide and / or a hydrolyzate thereof, and the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or A solution made of any of these mixtures is formed by coating. Other examples of the coating layer that imparts high gas barrier properties include those comprising a water-soluble polymer and tin chloride, and further comprising a solution comprising the water-soluble polymer coated with polyvinyl alcohol. Specifically, a solution in which a water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which a metal alkoxide is directly or previously hydrolyzed in the solution. The mixed solution is formed by coating the coating layer 114 made of a metal oxide and heating and drying.

  Each component forming the gas barrier coating 115 will be described in more detail.

  Specific examples of the water-soluble polymer used for forming the coating layer of the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, polyvinyl alcohol (hereinafter referred to as PVA) has the best gas barrier properties. The PVA here is generally obtained by saponifying polyvinyl acetate, from a so-called partially saponified PVA in which several tens percent of acetic acid groups remain to completely saponified PVA in which only several percent of acetic acid groups remain. Including, but not limited to.

The tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and may be used as an anhydride or a hydrate.

Further, the metal alkoxide may be a general formula such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], M (OR) _n (M : Metal such as Si, Ti, Al and Zr, R: alkyl group such as CH ₃ and C ₂ H ₅ ). Among these, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

  Each of the above components can be used alone or in combination to form a coating layer, and further within the range that does not impair the gas barrier properties of the coating layer, isocyanate compound, silane coupling agent, dispersant, stabilizer, viscosity adjustment You may add additives, such as an agent and a coloring agent.

  For example, the isocyanate compound added to the gas barrier coating 115 has two or more isocyanate groups (NCO groups) in the molecule. For example, tolylene diisocyanate (hereinafter referred to as TDI), triphenylmethane triisocyanate (hereinafter referred to as TTI). And monomers such as tetramethylxylene diisocyanate (hereinafter referred to as TMXDI) and polymers or derivatives thereof.

  Conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method and the like that are usually used can be used for the coating method for forming the gas barrier film 115. The thickness of the coating layer varies depending on the type of coating agent for forming the coating layer and the processing conditions, but it is sufficient that the thickness after drying is 0.01 μm or more, but if the thickness is 50 μm or more, the film will crack. Since it becomes easy, the range of 0.01-50 micrometers is preferable.

  It is also possible to laminate another layer on the coating layer 114 made of a metal oxide or the gas barrier coating 115. For example, a printing layer, an intervening film, a heat seal layer, and the like. The printed layer is formed for practical use as a packaging bag, etc., and various pigments are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, rubber and vinyl chloride. , A layer composed of an ink to which additives such as extender pigments, plasticizers, desiccants, stabilizers and the like are added, and characters, patterns, etc. are formed. As a forming method, for example, a well-known printing method such as an offset printing method, a gravure printing method, a silk screen printing method can be used for the printing layer, and a roll coating, a knife edge coating, a gravure coating, etc. can be used for the other layers. A well-known coating method can be used. The thickness may be 0.1 to 2.0 μm.

  In addition, the intervening film is provided to increase the bag breaking strength during boil and retort sterilization, and is generally biaxially stretched nylon film, biaxially stretched polyethylene terephthalate film, biaxially stretched from the standpoint of mechanical strength and thermal stability. Often selected from polypropylene films. The thickness is determined according to the material, required quality, and the like, but is generally in the range of 10 to 30 μm. As a forming method, lamination can be performed by a known method such as a dry laminating method in which an adhesive such as a two-component curable urethane resin is used.

  The heat seal layer is provided as a sealing layer when a bag-like package or the like is formed. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer or their metals A film made of one kind of resin such as a cross-linked product is used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. As a forming method, it is common to use a dry laminating method or the like in which a film forming a heat seal layer is bonded using an adhesive such as a two-component curable urethane resin. Can do.

  Examples of some embodiments of the present invention will be described below, but the present invention is not limited thereto.

<Preparation of coating liquid A1>
An aqueous solution containing a water-dispersible polyester polyurethane having adipic acid as a dibasic acid component of polyester and bisphenol A glycidyl ether in a solid mass ratio of 100: 6 was prepared. Hereinafter, this aqueous solution is referred to as “coating solution A1”.

<Preparation of coating solution B1>
A 6 g acrylic polyol solution containing an acrylic polyol having a hydroxyl value of 140 mgKOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.5 g of γ-isocyanatopropyltrimethoxysilane were mixed, and ethyl acetate was added to the mixture to make the solid content concentration 20% by mass. 7 g of this solution was weighed and mixed with 1.5 g of a mixture containing xylylene diisocyanate and isophorone diisocyanate in a mass ratio of 60:40. Next, this solution was diluted with ethyl acetate so that the solid content concentration was 2% by mass and further stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “coating liquid B1”.

<Preparation of coating solution B2>
A 6 g acrylic polyol solution containing an acrylic polyol having a hydroxyl value of 140 mgKOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.6 g of γ-aminopropyltriethoxysilane were mixed, and ethyl acetate was added to the mixture to make the solid content concentration 20% by mass. 7 g of this solution was weighed and mixed with 1.5 g of a mixture containing xylylene diisocyanate and isophorone diisocyanate in a mass ratio of 60:40. Next, this solution was diluted with ethyl acetate so that the solid content concentration was 2% by mass, and further stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “coating liquid B2”.

<Preparation of coating solution B3>
A 6 g acrylic polyol solution containing an acrylic polyol having a hydroxyl value of 140 mgKOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.6 g of bis (3-triethoxysilylpropyl) amine were mixed, and ethyl acetate was added to this mixed solution to make the solid content concentration 20% by mass. 7 g of this solution was weighed and mixed with 1.5 g of a mixture containing 0.75 g of xylylene diisocyanate and isophorone diisocyanate in a mass ratio of 60:40. Next, this solution was diluted with ethyl acetate so that the solid content concentration was 2% by mass, and further stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “coating liquid B3”.

<Preparation of coating solution B4>
A 6 g acrylic polyol solution containing an acrylic polyol having a hydroxyl value of 140 mgKOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.6 g of bis (3-trimethoxysilylpropyl) amine were mixed, and ethyl acetate was added to this mixed solution to make the solid content concentration 20% by mass. 7 g of this solution was weighed and mixed with 1.5 g of a mixture containing 0.75 g of xylylene diisocyanate and isophorone diisocyanate in a mass ratio of 60:40. Next, this solution was diluted with ethyl acetate so that the solid content concentration was 2% by mass, and further stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “coating liquid B4”.

<Preparation of coating solution B5>
A 7 g ethyl acetate solution containing a polyester resin having a hydroxyl value of 7 mg KOH / g at a concentration of 50% by mass was prepared. To this solution, 1.5 g of a mixture containing xylylene diisocyanate and isophorone diisocyanate in a mass ratio of 60:40 was mixed. Next, this solution was diluted with ethyl acetate so that the solid content concentration was 2% by mass and further stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “coating liquid B5”.
<Preparation of coating solution b1>
An equal amount of bis (3-triethoxysilylpropyl) amine and vinyltriethoxysilane was mixed, and this mixed solution was added to a mixture of water and ethanol to prepare a solid content of 10%. Hereinafter, this aqueous solution is referred to as “coating liquid b1”.

<Preparation of coating liquid b2>
Bis (3-triethoxysilylpropyl) amine and vinyltriethoxysilane were mixed in equal amounts, and this mixed solution was added to a mixture of water and ethanol to prepare a solid content of 5%. Hereinafter, this aqueous solution is referred to as “coating liquid b2”.

<Preparation of coating liquid b3>
Bis (3-triethoxysilylpropyl) amine and vinyltriethoxysilane were mixed in equal amounts, and this mixture was added to a mixture of water and ethanol to prepare a solid content of 15%. Hereinafter, this aqueous solution is referred to as “coating liquid b3”.

<Preparation of coating liquid b4>
Bis (3-triethoxysilylpropyl) amine and methyltriethoxysilane were mixed in equal amounts, and this mixed solution was added to a mixture of water and ethanol to prepare a solid content of 10%. Hereinafter, this aqueous solution is referred to as “coating liquid b4”.
<Preparation of coating liquid b5>
Bis (3-trimethoxysilylpropyl) amine and vinyltriethoxysilane were mixed in equal amounts, and this mixed solution was added to a mixture of water and ethanol to prepare a solid content of 10%. Hereinafter, this aqueous solution is referred to as “coating liquid b5”.

<Preparation of coating liquid b6>
Bis (3-trimethoxysilylpropyl) amine was added to a mixture of water and ethanol to prepare a solid content of 10%. Hereinafter, this aqueous solution is referred to as “coating liquid b6”.

<Preparation of coating liquid C1>
To 10 g of tetraethoxysilane, 90 g of 0.1N hydrochloric acid aqueous solution was added. Next, this mixed solution was stirred for 30 minutes to cause hydrolysis of tetraethoxysilane. Thus, to obtain a hydrolysis solution containing a concentration of 3 wt% solids in terms of SiO _2.

  PVA, water and isopropyl alcohol were mixed to prepare a 65 g PVA solution. The mass ratio of water to isopropyl alcohol was 90:10. The PVA concentration of this PVA solution was 4% by mass.

  These hydrolysis solution and PVA solution were mixed to prepare a coating solution. Hereinafter, this coating solution is referred to as “coating solution C1”.

<Preparation of coating liquid C2>
17.9 g of tetraethoxysilane, 10 g of methanol, and 72.1 g of 0.1N aqueous hydrochloric acid were mixed. Next, this mixed solution was stirred for 30 minutes to cause hydrolysis of tetraethoxysilane. As a result, a hydrolysis solution containing a solid content of 5% by mass in terms of SiO ₂ was obtained. Hereinafter, this hydrolysis solution is referred to as “solution S1”.

  PVA, water, and isopropyl alcohol were mixed to prepare a PVA solution. The mass ratio of water to isopropyl alcohol was 95: 5. Further, the solid content concentration of the PVA solution, that is, the PVA concentration was set to 5% by mass. Hereinafter, this PVA solution is referred to as “solution S2”.

1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate, water and isopropyl alcohol were mixed. The mass ratio of water to isopropyl alcohol was 50:50. The concentration of 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate in this mixed solution was 5% by mass in terms of R ₂ Si (OH) ₃ . The mixture was then stirred for 30 minutes to cause hydrolysis of 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate. As a result, a hydrolyzed solution containing a solid content of 5% by mass in terms of R ₂ Si (OH) ₃ was obtained. Hereinafter, this hydrolysis solution is referred to as “solution S3”.

  Thereafter, the solution S1, the solution S2, and the solution S3 were mixed so that the mass ratio of the solid contents was 70:20:10. Hereinafter, this liquid mixture is referred to as “coating liquid C2”.

<Preparation of coating liquid C3>
A 1N hydrochloric acid aqueous solution was gradually added to an isopropyl alcohol solution of γ-glycidoxyprovir trimethoxysilane. The mass ratio of water to isopropyl alcohol was 50:50. The concentration of γ- glycidoxypropyltrimethoxysilane professional buildings trimethoxysilane in the mixture was 5 mass% in R ₂ Si (OH) ₃ reduced concentration. The mixture was then stirred for 30 minutes to cause hydrolysis of γ-glycidoxyprovir trimethoxysilane. As a result, a hydrolyzed solution containing a solid content of 5% by mass in terms of R ₂ Si (OH) ₃ was obtained. Hereinafter, this hydrolysis solution is referred to as “solution S4”.

Thereafter, the solution S1, the solution S2, and the solution S4 are mixed at a mass ratio of 70:20:
The mixture was mixed to 10. Hereinafter, this liquid mixture is referred to as “coating liquid C3”.

<Manufacture of transparent gas barrier film BF1 and transparent packaging material PM1>
First, an unstretched substrate film made of nylon 6 and having a thickness of 150 μm was formed by a T-die method.

  Next, the coating liquid A1 was applied on one main surface of the base film by the Meyer bar coating method. After the coating film was dried, the base film was simultaneously biaxially stretched 3.0 times in the longitudinal direction and 3.3 times in the transverse direction. Furthermore, the heat setting process was performed at the temperature of 210 degreeC. Thus, while making the thickness of a base film into 15 micrometers, the easily bonding layer whose thickness is 0.05 micrometer was formed on it.

  Then, coating liquid B1 was apply | coated by the gravure coating method on the easily bonding layer. By drying this coating film, an anchor coat layer having a thickness of 0.05 μm was obtained.

  Then, the 15-nm-thick inorganic oxide layer which consists of aluminum oxide was formed on the easily bonding layer with the vacuum evaporation system using an electron beam heating system.

  Next, the coating liquid C1 was apply | coated on the inorganic oxide layer by the gravure coating method. This coating film was dried by heating to obtain a gas barrier coating film having a thickness of 0.3 μm.

  As described above, a transparent gas barrier film was completed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF1”.

Next, the transparent gas barrier film BF1 and the heat sealable resin layer were bonded together by a dry lamination method so that the heat sealable resin layer faced the gas barrier film. As the heat-sealable resin layer, a 50 μm-thick linear low-density polyethylene film (manufactured by Tosero Co., Ltd., TUX-FCS) is used, and the adhesive is a two-component curable polyurethane-based laminate adhesive (Mitsui Chemical polyurethane, A515 / A50) was used. The adhesive was applied on the gas barrier coating by gravure coating so that the coating amount after drying was 4.0 g / m ² .

   Thereafter, this laminate was cured in a constant temperature room at 40 ° C. for 7 days. The transparent packaging material was completed as mentioned above. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM1”.

<Manufacture of transparent gas barrier film BF2 and transparent packaging material PM2>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1, except that the thickness of the easy adhesion layer was 0.20 μm. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF2”.

    Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF2 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM2”.

<Manufacture of transparent gas barrier film BF3 and transparent packaging material PM3>
Transparent gas barrier film BF1 except that an anchor coat layer having a thickness of 0.1 μm was formed by using coating liquid B2 instead of forming an anchor coat layer having a thickness of 0.05 μm by using coating liquid B1. A transparent gas barrier film was produced by the same method as described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF3”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF3 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM3”.

<Manufacture of transparent gas barrier film BF4 and transparent packaging material PM4>
Transparent gas barrier film BF1 except that an anchor coat layer having a thickness of 0.1 μm was formed by using coating liquid B3 instead of forming an anchor coat layer having a thickness of 0.05 μm by using coating liquid B1. A transparent gas barrier film was produced by the same method as described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF4”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF4 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM4”.

<Manufacture of transparent gas barrier film BF5 and transparent packaging material PM5>
Transparent gas barrier film BF1 except that an anchor coat layer having a thickness of 0.1 μm was formed by using coating liquid B4 instead of forming an anchor coat layer having a thickness of 0.05 μm by using coating liquid B1. A transparent gas barrier film was produced by the same method as described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF5”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF5 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM5”.

<Manufacture of transparent gas barrier film BF6 and transparent packaging material PM6>
The transparent gas barrier film BF1 except that instead of forming a gas barrier film having a thickness of 0.3 μm using the coating liquid C1, a gas barrier film having a thickness of 0.5 μm was formed using the coating liquid C2. A transparent gas barrier film was produced by the same method as described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF6”.

Next, instead of the transparent gas barrier film BF1, the transparent gas barrier film BF6
A transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that was used. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM6”.

<Manufacture of transparent gas barrier film BF7 and transparent packaging material PM7>
The coating liquid B2 is used instead of the coating liquid B1 to form an anchor coat layer, and the coating liquid C1 is used to form a gas barrier film having a thickness of 0.3 μm. A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1, except that a 0.5 μm gas barrier film was formed. That is, a transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF6 except that the coating liquid B2 was used instead of the coating liquid B1 to form the anchor coat layer. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF7”.

Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF7 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM7”.

<Manufacture of transparent gas barrier film BF8 and transparent packaging material PM8>
The coating liquid B3 is used instead of the coating liquid B1 to form an anchor coat layer, and the coating liquid C1 is used to form a gas barrier film having a thickness of 0.3 μm. A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1, except that a 0.5 μm gas barrier film was formed. That is, a transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF6 except that the coating liquid B3 was used instead of the coating liquid B1 to form the anchor coat layer. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF8”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF8 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM8”.

<Manufacture of transparent gas barrier film BF9 and transparent packaging material PM9>
The coating liquid B4 is used instead of the coating liquid B1 to form an anchor coat layer, and the coating liquid C1 is used to form a gas barrier film having a thickness of 0.3 μm. A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1, except that a 0.5 μm gas barrier film was formed. That is, a transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF6 except that the coating liquid B4 was used instead of the coating liquid B1 to form the anchor coat layer. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF9”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF9 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM9”.

<Manufacture of transparent gas barrier film BF10 and transparent packaging material PM10>
The transparent gas barrier film BF1 except that instead of forming a gas barrier film having a thickness of 0.3 μm using the coating liquid C1, a gas barrier film having a thickness of 0.5 μm was formed using the coating liquid C3. A transparent gas barrier film was produced by the same method as described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF10”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF10 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM10”.

<Manufacture of transparent gas barrier film BF11 and transparent packaging material PM11>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1 except that the easy adhesion layer was omitted. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF11”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF11 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM11”.

<Manufacture of transparent gas barrier film BF12 and transparent packaging material PM12>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1 except that the anchor coat layer was omitted. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF12”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF12 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM12”.

<Manufacture of transparent gas barrier film BF13 and transparent packaging material PM13>
A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film BF1 except that the coating liquid B5 was used instead of the coating liquid B1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF13”.

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material PM1 except that the transparent gas barrier film BF13 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM13”.

<Manufacture of transparent gas barrier film bF1 and transparent packaging material pM1>
First, an unstretched substrate film made of nylon 6 and having a thickness of 150 μm was formed by a T-die method.

  Next, the coating liquid A1 was applied on one main surface of the base film by the Meyer bar coating method. After the coating film was dried, the base film was simultaneously biaxially stretched 3.0 times in the longitudinal direction and 3.3 times in the transverse direction. Furthermore, the heat setting process was performed at the temperature of 210 degreeC. Thus, while making the thickness of a base film into 15 micrometers, the easily bonding layer whose thickness is 0.05 micrometer was formed on it.

  Then, coating liquid B1 was apply | coated by the gravure coating method on the easily bonding layer. By drying this coating film, an anchor coat layer having a thickness of 0.05 μm was obtained.

  Then, the 15-nm-thick inorganic oxide layer which consists of aluminum oxide was formed on the easily bonding layer with the vacuum evaporation system using an electron beam heating system.

  Next, the coating liquid C1 was apply | coated on the inorganic oxide layer by the gravure coating method. This coating film was dried by heating to obtain a gas barrier coating film having a thickness of 0.3 μm.

  As described above, a transparent gas barrier film was completed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF1”.

Next, the transparent gas barrier film bF1 and the heat sealable resin layer were bonded together by a dry lamination method so that the heat sealable resin layer faced the gas barrier film. As the heat-sealable resin layer, a 50 μm-thick linear low-density polyethylene film (manufactured by Tosero Co., Ltd., TUX-FCS) is used, and the adhesive is a two-component curable polyurethane-based laminate adhesive (Mitsui Chemical polyurethane, A515 / A50) was used. The adhesive was applied on the gas barrier coating by gravure coating so that the coating amount after drying was 4.0 g / m ² .

  Thereafter, this laminate was cured in a constant temperature room at 40 ° C. for 7 days. The transparent packaging material was completed as mentioned above. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM1”.

<Manufacture of transparent gas barrier film bF2 and transparent packaging material pM2>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film bF1 except that the thickness of the anchor coat layer was 0.10 μm. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF2.”

   Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF2 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM2.”

<Manufacture of transparent gas barrier film bF3 and transparent packaging material pM3>
The transparent gas barrier film is formed in the same manner as described for the transparent gas barrier film bF1, except that the anchor coat layer is formed using the coating liquid B2 instead of forming the anchor coat layer using the coating liquid B1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF3”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF3 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM3”.

<Manufacture of transparent gas barrier film bF4 and transparent packaging material pM4>
The transparent gas barrier film is the same as described for the transparent gas barrier film bF1 except that the anchor coat layer is formed using the coating liquid B3 instead of forming the anchor coat layer using the coating liquid B1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF4”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF4 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM4”.

<Manufacture of transparent gas barrier film bF5 and transparent packaging material pM5>
The transparent gas barrier film is the same as described for the transparent gas barrier film bF1 except that the anchor coat layer is formed using the coating liquid B4 instead of forming the anchor coat layer using the coating liquid B1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF5”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF5 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM5”.

<Manufacture of transparent gas barrier film bF6 and transparent packaging material pM6>
The transparent gas barrier film was formed in the same manner as described for the transparent gas barrier film bF1 except that the anchor coat layer was formed using the coating liquid B5 instead of forming the anchor coat layer using the coating liquid B1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF6”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF6 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM6”.

<Manufacture of transparent gas barrier film bF7 and transparent packaging material pM7>
The transparent gas barrier film is formed in the same manner as described for the transparent gas barrier film bF1 except that the gas barrier film is formed using the coating liquid C2 instead of forming the gas barrier film using the coating liquid C1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF7”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF7 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM7”.

<Manufacture of transparent gas barrier film bF8 and transparent packaging material pM8>
The transparent gas barrier film is formed in the same manner as described for the transparent gas barrier film bF5 except that the gas barrier film is formed using the coating liquid C2 instead of forming the gas barrier film using the coating liquid C1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF8”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF8 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM8”.

<Manufacture of transparent gas barrier film bF9 and transparent packaging material pM9>
The transparent gas barrier film is formed in the same manner as described for the transparent gas barrier film bF6 except that the gas barrier film is formed using the coating liquid C2 instead of forming the gas barrier film using the coating liquid C1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF9”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF9 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM9”.

<Manufacture of transparent gas barrier film bF10 and transparent packaging material pM10>
Instead of forming an inorganic oxide layer made of aluminum oxide having a thickness of 15 nm by a vacuum vapor deposition apparatus using an electron beam heating method, an inorganic film having a thickness of 50 nm made of silicon oxide by a vacuum vapor deposition apparatus using a resistance heating method. The same method as described for the transparent gas barrier film bF1 except that the oxide layer is formed and the gas barrier film is formed using the coating liquid C2 instead of forming the gas barrier film using the coating liquid C1. Thus, a transparent gas barrier film was produced. That is, instead of forming an inorganic oxide layer made of aluminum oxide having a thickness of 15 nm by a vacuum vapor deposition apparatus using an electron beam heating method, the thickness made of silicon oxide by a vacuum vapor deposition apparatus using a resistance heating method is 50 nm. A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film bF7 except that the inorganic oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF10”.

Next, instead of the transparent gas barrier film bF1, the transparent gas barrier film bF1
A transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that 0 was used. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM10”.

<Manufacture of transparent gas barrier film bF11 and transparent packaging material pM11>
The transparent gas barrier film is formed in the same manner as described for the transparent gas barrier film bF1 except that the gas barrier film is formed using the coating liquid C3 instead of forming the gas barrier film using the coating liquid C1. Manufactured. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF11”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF11 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM11”.

<Manufacture of transparent gas barrier film bF12 and transparent packaging material pM12>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film bF1 except that the easy adhesion layer was omitted. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF12”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF12 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM12”.

<Manufacture of transparent gas barrier film bF13 and transparent packaging material pM13>
A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film bF1 except that the anchor coat layer was omitted. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF13”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF13 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM13”.

<Manufacture of transparent gas barrier film bF14 and transparent packaging material pM14>
A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film bF1 except that the coating liquid B6 was used instead of the coating liquid B1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film bF14”.

  Next, a transparent packaging material was produced by the same method as described for the transparent packaging material pM1 except that the transparent gas barrier film bF14 was used instead of the transparent gas barrier film bF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material pM14”.

<Measurement of heat seal energy>
About each of the manufactured transparent packaging materials, the heat seal strength was measured in accordance with a test method defined in Japanese Industrial Standards JIS Z1707: 1997 “General Rules for Plastic Films for Food Packaging”. Thereafter, the heat seal energy was obtained from the chart obtained by the measurement.

That is, first, a sample having a size of 100 mm × 100 mm was cut out from each of the transparent packaging materials. Next, the sample is folded at the center, and a heat seal tester (tester industry (
The product was sealed at a seal bar width of 5 mm, a pressure of 2 kg / cm ² and a temperature of 180 ° C. for 1 second, and then allowed to cool. After soaking them in water for 12 hours, they were taken out of the water, and a strip-shaped test piece having a width of 15 mm was prepared from each sample. Subsequently, the seal part was peeled off at 30 mm / min with a tensile tester, and the heat seal strength was measured. Next, the heat seal energy was derived from the chart obtained by measuring the heat seal strength. In the present invention, the area surrounded by the curve indicating the heat seal strength and the chart moving distance is defined as the heat seal energy (N · m). Table 1 below summarizes the measurement results of the transparent packaging materials PM1 to PM13, and Table 3 summarizes the measurement results of the transparent packaging materials pM1 to PM14.

<Measurement of oxygen permeability>
About each of the manufactured transparent gas barrier film, oxygen permeability was measured according to the B method (isobaric method) prescribed | regulated by Japanese Industrial Standards JIS K7126-1987 "The gas permeability test method of a plastic film and a sheet | seat." This measurement was performed using an Oxford 2/21 manufactured by Modern Control in an environment where the temperature was 30 ° C. and the relative humidity was 70%. Table 1 below summarizes the measurement results of the transparent gas barrier films BM1 to BM13, and Table 3 summarizes the measurement results of the transparent gas barrier films bM1 to bM14.

<Measurement of wet laminate strength>
For each of the transparent packaging materials, the wet laminate strength was measured in accordance with the test method defined in Japanese Industrial Standards JIS K6854-3: 1999 “Adhesive—Peeling peel strength test method—Part 3: T-shaped peel”.

  That is, first, a strip-shaped test piece having a width of 15 mm was prepared from each of the transparent packaging materials. Next, the heat-sealable resin layer and the transparent gas barrier film were peeled from each other at one end of each test piece, and each was attached to a gripping tool of a tensile tester. After that, applying a tensile stress while moistening the peeling interface with water, the heat-sealable resin layer and the transparent gas barrier film are peeled from each other, and the relationship between the peeling length (grasping movement distance) and the tensile stress is recorded. did. Here, the peeling speed was 300 mm / min. And average peeling force (N) was calculated | required from the force-grasping movement distance curve over the peeling length of 100 mm or more except the first and the last 25 mm. This average peel force (N) was defined as the wet laminate strength. Table 1 below summarizes the measurement results of the transparent packaging materials PM1 to PM13, and Table 3 summarizes the measurement results of the transparent packaging materials pM1 to pM14.

<Measurement of oxygen permeability after boiling treatment>
Using each of the transparent packaging materials, a four-side sealed bag having a size of 100 mm × 150 mm was prepared. Each four-sided seal bag was filled with 150 g of water. Next, these packages were subjected to a boiling treatment at 95 ° C. for 30 minutes. After being left overnight, the oxygen permeability was measured by the same method as described above. Table 2 below summarizes the measurement results of the transparent packaging materials PM1 to PM13, and Table 4 summarizes the measurement results of the transparent packaging materials pM1 to pM14.

<Measurement of normal or wet laminate strength after boiling treatment>
Using each of the transparent packaging materials, a four-side sealed bag having a size of 100 mm × 150 mm was prepared. Each four-sided seal bag was filled with 150 g of water. Next, these packaged products were subjected to a boiling treatment at 95 ° C. for 30 minutes, and then the normal laminate strength was measured for the transparent packaging materials PM1 to PM13 and the wet laminate strength was measured for the transparent packaging materials pM1 to pM14.
Specifically, the average peel force (N) was determined by the same method as described for the wet laminate strength except that the peel interface was not wetted with water, and this average peel force (N) was determined as the normal laminate strength. It was. The normal laminate strength was measured within 1 hour after the boiling treatment was completed. Table 2 below summarizes the measurement results of the transparent packaging materials PM1 to PM13, and Table 4 summarizes the measurement results of the transparent packaging materials pM1 to pM14.

表１および表２に示すように、比較例の透明包装材料ＰＭ１１ないしＰＭ１３は、ヒートシール強度のエネルギー値、湿潤ラミネート強度ならびに煮沸処理後における常態ラミネート強度が低かった。

As shown in Tables 1 and 2, the transparent packaging materials PM11 to PM13 of Comparative Examples had low energy values for heat seal strength, wet laminate strength, and normal laminate strength after boiling.

In contrast, the transparent packaging materials PM1 to PM10 of the present invention had higher energy values for heat seal strength, wet laminate strength, and normal laminate strength after boiling compared with the transparent packaging materials PM11 to PM13 of the comparative examples. .
As shown in Tables 3 and 4, the transparent packaging materials pM12 to pM14 of the comparative examples had low energy values for heat seal strength, wet laminate strength, and normal laminate strength after boiling.
In contrast, the transparent packaging materials pM1 to pM11 of the present invention had higher energy values for heat seal strength, wet laminate strength, and normal laminate strength after boiling compared with the transparent packaging materials pM12 to pM14 of the comparative examples. .
By using the transparent gas barrier film of the present invention, the adhesiveness between the base film made of polyamide resin and the inorganic oxide layer, particularly when wet, was improved. As a result, it was possible to prevent the entire laminated film from being easily stretched due to a decrease in the adhesion between the films when the liquid-containing contents were packaged, and easily breaking. Judging this from the numerical value of heat seal energy, which is an index of the ease of elongation of the packaging material film, it was possible to set a range in which packaging breakage hardly occurs.

The cross-sectional schematic diagram which shows schematically the transparent packaging material which concerns on one form of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Transparent packaging material 11 ... Transparent gas barrier film 12 ... Adhesive layer 13 ... Heat-sealable resin layer 111 ... Base film 112 ... Easy-adhesion layer 113 ... Anchor coat layer 114 ... Inorganic oxide layer 115 ... Gas barrier film

Claims (11)

An easy-adhesion layer is provided on at least one surface of the polyamide-based resin base material layer, an anchor coat layer is provided on the easy-adhesion layer, and a coating layer made of a metal oxide formed on the anchor coat layer by vapor deposition When the gas barrier film has a laminated structure in which the surface of the coating layer of the gas barrier film and the sealant layer are laminated, the sealant layer is thermally fused and immersed in water. A gas barrier film characterized in that the maximum energy value of the heat seal strength measured after JIS Z1707 is 0.03 to 0.5 N · m. The gas barrier film according to claim 1, wherein the easy-adhesion layer contains nitrogen atoms, adipic acid, and bisphenol glycidyl ether. The gas barrier film according to claim 1 or 2, wherein the anchor coat layer contains a reaction product of an acrylic polyol, an isocyanate compound, and a metal alkoxide or a hydrolysis product thereof. The gas barrier according to claim 1 or 2, wherein the anchor coat layer contains at least two or more metal alkoxides, and one of the metal alkoxides uses an alkoxysilane having an amino group. Sex film. The gas barrier film according to any one of claims 1 to 4, wherein the coating layer made of the metal oxide is made of any one of aluminum oxide, silicon oxide, magnesium oxide, and a mixture thereof. The gas barrier coating film comprising a mixture containing a transparent resin and an inorganic substance is provided on the coating layer comprising the metal oxide of the film according to claim 1. Film. The gas barrier coating is formed by applying a solution containing a water-soluble polymer, tetraalkoxysilane or a hydrolysis product thereof and trialkoxysilane or a hydrolysis product onto the coating layer made of the metal oxide. The gas barrier film according to claim 6, wherein the gas barrier film is formed by drying a coating film obtained by the above process. 8. The gas barrier film according to claim 7, wherein the organic functional group other than the alkoxy group bonded to silicon of the trialkoxysilane is a hydrophobic organic functional group. The gas barrier coating comprises a solution containing water, a water-soluble polymer, a metal alkoxide, a hydrolysis product thereof, and at least one compound selected from the group consisting of tin chloride on the inorganic oxide layer. The gas barrier film according to claim 6, wherein the gas barrier film is formed by applying to a substrate and drying the coating film obtained thereby. The gas barrier film according to any one of claims 1 to 9, and a heat-sealable resin layer that is bonded to the gas barrier film and faces the base film with the inorganic oxide layer interposed therebetween. A transparent packaging material characterized by comprising: A package comprising the transparent packaging material according to claim 10.

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