JP5104227B2 - Gas barrier film, packaging material, and package - Google Patents

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 oils and the like 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 a metal foil such as an aluminum foil, a polyvinylidene chloride (PVDC) layer, a saponified ethylene-vinyl alcohol copolymer (EVOH) layer, and a 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 substrate 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 decreases, 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.
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.

According to the first aspect of the present invention, a base film made of a polyamide resin, an easy-adhesion layer formed on one main surface of the base film and containing nitrogen atoms, adipic acid and bisphenol glycidyl ether, An anchor coat layer formed on the easy-adhesion layer and containing a reaction product of a composition containing a polyol and an isocyanate compound; an inorganic oxide layer formed on the anchor coat layer by a vapor deposition method; When the positive and negative secondary ion mass spectrum analysis of the easy-adhesion layer with a time-of-flight secondary ion mass spectrometer was performed, a peak of CNO ⁻ as a peak derived from a nitrogen atom-containing component , and adipine C ₆ H ₇ O ₂ as peaks derived from acid components ^- and C ₆ H ₉ O ₃ ^- and the peak of, C ₉ as a peak group derived from bisphenol glycidyl ether component A transparent gas barrier film characterized in that peaks of H ₁₁ O ⁺ , C ₁₄ H ₁₃ O ₂ ⁺ and C ₁₄ H ₁₁ O ₂ ⁻ are detected is provided.

  According to the second aspect of the present invention, the gas barrier film according to the first aspect and the heat-sealable resin layer bonded to the gas barrier film and facing the base film with the inorganic oxide layer interposed therebetween A transparent packaging material characterized by comprising:

  According to the 3rd side surface of this invention, the packaging body characterized by having comprised the packaging material which concerns on a 2nd side surface is provided.

  According to this invention, the adhesiveness of the inorganic oxide layer with respect to the base film which consists of a polyamide resin can be improved.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, in each figure, the same referential mark is attached | subjected to the component which exhibits the same or similar function, and the overlapping description is abbreviate | 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, an inorganic oxide layer 114, 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), polylaurin lactam (nylon). 12), polyethylenediamine adipamide (nylon 2,6), polytetramethylene adipamide (nylon 4,6), polyhexamethylenediadipamide (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), Alternatively, metaxylenediamine-6 nylon (MXD6) can be used.

  Examples of the copolyamide include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium sebacate copolymer, hexamethylene diammonium adipate / hexamethylene diammonium Sebacate copolymers or caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymers 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, a lactam, 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.

When positive and negative secondary ion mass spectrum analysis of the easy-adhesion layer 112 using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) was performed, the analysis results were as follows: nitrogen atom-containing component, adipic acid component, The presence of a bisphenol glycidyl ether component is indicated. For example, when a positive and negative secondary ion mass spectrum of the easy-adhesion layer 112 by TOF-SIMS is performed, a peak of CNO ⁻ as a peak derived from a nitrogen atom-containing component and a peak group derived from an adipic acid component as C and peak, C ₉ H ₁₁ O ⁺ as peaks derived from bisphenol glycidyl ether component, C ₁₄ H ₁₃ O ₂ ⁺ and _{^{C 14 H 11 O 2 - -}} 6 H 7 O 2 - and C ₆ H ₉ O ₃ of A peak is detected.

  More specifically, 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, and a water-dispersible polyester polyurethane polyurea resin containing adipic acid as a polyester dibasic acid. , The prepolymer, or a mixture containing two or more thereof 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 end of the reactive organism 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, a Meyer bar coat method, or an inverse roll 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. . The latter method is more productive and efficient than the former method. In the latter method, since the easy-adhesion layer 112 is heat-treated at a high temperature in this stretch film formation step, the adhesion between the base film 111 and the easy-adhesion layer 112 is strengthened as compared with the former method. Can do.

  Examples of the method for forming the easy-adhesion layer 112 during the stretch film formation step include the following methods. First, the polyamide-based resin is heated and melted with an extruder and extruded into a film shape, and an unstretched polyamide-based 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 easily bonding layer 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-based resin is heated and melted with an extruder and extruded into a film shape, and an unstretched polyamide-based resin film is formed as a base film 111. Next, the base film 111 is passed through heating rollers having different peripheral speeds to perform longitudinal stretching. Subsequently, a coating liquid for forming the easy-adhesion layer 112 is applied onto the longitudinally stretched substrate film 111, the coating film is dried and preheated, and then the substrate film 111 is subjected to a transverse stretching process together with the coating film. . Furthermore, the easily bonding layer 112 formed on the base film 111 is obtained by performing a heat setting process.

  The thickness of the easy adhesion layer 112 is, for example, in the range of 0.01 μm to 0.2 μm. It is difficult to form the thin easy-adhesion layer 112 as a continuous film having a uniform thickness, and it is difficult to obtain sufficient adhesion. Moreover, when the easy-adhesion layer 112 is made thick to some extent, the effect of improving the adhesion due to the 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. Anchor coat layer 113 contains a reaction product of a composition containing 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.

  The silane coupling agent or the hydrolysis product thereof typically has an organic functional group that reacts with a hydroxyl group of a polyol and / or an isocyanate group of an isocyanate compound. Examples of such silane coupling agents include compounds having an isocyanate group such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane, and mercapto groups such as γ-mercaptopropyltriethoxysilane. Compounds having, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, and γ-phenylaminopropyltrimethoxysilane, etc. A compound having an amino group, a compound having an epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or vinyltrimethoxysilane Or vinylt It can be used scan (beta-methoxyethoxy) by the action of alcohol to a silane coupling agent having a vinyl group such as hydroxyl and made by adding compounds such as silane. 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, and thereby the cohesive force of the anchor coat layer 113 is increased. Increase. In addition, the alkoxy group of the silane coupling agent or the silanol group generated by hydrolysis thereof strongly interacts with polar groups such as a metal contained in the inorganic oxide layer 114 and a hydroxyl group existing on the surface of the inorganic oxide. Thus, the adhesion between the anchor coat layer 113 and the inorganic oxide layer 114 is improved.

  The silane coupling agent is typically a compound in which an alkoxy group and other organic functional group are bonded to a silicon atom, but a compound in which the alkoxy group is substituted with a halogen group or an acetoxy group is used. May be. That is, what is necessary is just to produce a silanol group by hydrolysis. 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. As the acrylic polyol, for example, an acrylic polyol obtained by polymerizing an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate; and this acrylic acid derivative monomer and other monomers such as styrene; Acrylic polyol obtained by copolymerizing can be used.

  The acrylic polyol is reacted with the isocyanate group of the isocyanate compound. In view of 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 may be used.

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

  The isocyanate compound reacts with the acrylic polyol to form a urethane bond, contributes to the adhesion between the anchor coat layer 113, the easy-adhesion layer 112 and the inorganic oxide layer 114, and acts mainly as a crosslinking agent or a curing agent. To do. Such an isocyanate compound is an aromatic or aliphatic diisocyanate or a tri- or higher polyisocyanate. This isocyanate compound may be either a low molecular compound or a high molecular compound.

  As the isocyanate compound, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexyl diisocyanate, or a trimer thereof. The body can be used. Alternatively, an excess amount of these isocyanate compounds and, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine and triethanolamine and other low molecular active hydrogen compounds, or polyester polyols, You may use the terminal isocyanate group containing compound obtained by making it react with active hydrogen polymer compounds, such as polyether polyol and polyamide.

  When the compounding ratio of the isocyanate compound with respect to the acrylic polyol is small, poor curing may occur. Moreover, when this compounding ratio is large, blocking etc. may be produced. This blending ratio is typically such that the isocyanate group and the hydroxyl group are equivalent so that the molar ratio of the isocyanate group derived from the isocyanate compound to the hydroxyl group derived from the acrylic polyol is 50 times or less. Set as follows.

  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, by mixing a silane coupling agent, an acrylic polyol and a solvent, reacting the silane coupling agent and the acrylic polyol, adding a solvent to the mixture, and further mixing the mixture with an isocyanate compound. can get.

  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 liquid, for example, in order to improve wettability and / or adhesion, the surface of the easy-adhesion layer 112 may be pretreated. 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.

When the anchor coat layer 113 thus formed was subjected to positive and negative secondary ion mass spectral analysis by TOF-SIMS, the analysis results were as follows: aromatic hydrocarbon component, nitrogen atom-containing component, and methacrylate component. And the presence of a silane compound component. For example, when positive and negative secondary ion mass spectra of the anchor coat layer 113 by TOF-SIMS are performed, C ₇ H ₇ ⁺ , C ₈ H ₉ ⁺ , as peak groups derived from aromatic hydrocarbon components, Peaks of C ₉ H ₇ ⁺ and C ₁₀ H ₉ ⁺ , peaks of CN ⁻ and CNO ⁻ as a peak group derived from a nitrogen atom-containing component, and C ₄ H ₅ O ⁺ and C ₄ H as a peak group of a methacrylate component A peak of ₅ O ₂ ⁻ and peaks of C ₂ H ₇ O ₂ Si ⁺ and C ₃ H ₉ O ₃ Si ⁺ are detected as a peak group derived from the silane compound component.

  The inorganic oxide layer 114 is a gas barrier transparent layer formed on the anchor coat layer 113 by a vapor deposition method. As a material of the inorganic oxide layer 114, for example, silicon oxide, aluminum oxide, tin oxide, magnesium oxide, or a mixture thereof can be used.

  For the formation of the inorganic oxide layer 114, for example, a vacuum evaporation method, a sputtering method, an ion plating method, or a plasma chemical vapor deposition method can be used. When the vacuum deposition method is used, for example, electron beam heating, resistance heating, or induction heating can be used for heating the evaporation material. When electron beam heating is used, the degree of freedom in selecting the evaporation material is great. When a plasma assist method or an ion beam assist method is used for vapor deposition, a denser inorganic oxide layer 114 can be formed. In addition, when reactive vapor deposition in which a gas such as oxygen is blown during vapor deposition is used, the inorganic oxide layer 114 having excellent transparency can be formed.

  When the inorganic oxide layer 114 is thin, it is difficult to form the inorganic oxide layer 114 as a continuous film having a uniform thickness, and sufficient gas barrier properties cannot be obtained. The thick inorganic oxide layer 114 has low flexibility, and may crack when the transparent gas barrier film 11 is bent or pulled. Further, the vapor deposition method is not suitable for forming a thick film from an economical viewpoint. The thickness of the inorganic oxide layer 114 is, for example, in the range of 5 nm to 500 nm.

  The gas barrier coating 115 is a transparent layer formed on the inorganic oxide layer 114. The gas barrier coating 115 is made of a mixture containing a transparent resin and an inorganic material such as an inorganic oxide. The gas barrier coating 115 can be omitted, but when the gas barrier coating 115 is provided, the transparent packaging material 10 having higher gas barrier properties can be obtained.

  For example, the gas barrier coating 115 is formed by applying a coating liquid containing a water-soluble polymer and a metal alkoxide and / or a hydrolysis product thereof and water on the inorganic oxide layer 114 and heating the coating. Obtained by drying. Alternatively, the gas barrier coating 115 is obtained, for example, by applying a coating solution containing water and a water-soluble polymer and tin chloride on the inorganic oxide layer 114, and heating and drying the coating. It is done. Alternatively, for example, the gas barrier coating 115 is formed by applying a coating solution containing water and a water-soluble polymer, a metal alkoxide and / or a hydrolysis product thereof, and tin chloride on the inorganic oxide layer 114. It is obtained by heating and drying the coating film. In addition, as a solvent of this coating liquid, water or the liquid mixture of water and alcohol can be used, for example.

  As the water-soluble polymer, for example, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, or a mixture thereof can be used. In particular, when PVA is used, the gas barrier coating 115 having the most excellent gas barrier properties can be formed. In addition, PVA here is typically obtained by saponifying polyvinyl acetate. As this PVA, various saponified PVA can be used from partially saponified PVA in which several tens% of acetyl groups remain to fully saponified PVA in which only several% of acetyl groups remain. There is no restriction | limiting in the molecular weight of PVA, For example, what has a polymerization degree in the range of 300 thru | or several thousand can be used. In general, a high molecular weight PVA having a high degree of saponification and a high degree of polymerization achieves excellent water resistance.

A metal alkoxide 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.

As the metal alkoxide, for example, tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] or triisopropoxyaluminum [Al (OCH (CH ₃ ) ₂ ) ₃ ] can be used. The hydrolysis products of tetraethoxysilane and triisopropoxyaluminum can exist relatively stably in water-containing solutions.

When alkoxysilane is used as the metal alkoxide, for example, a compound represented by the general formula Si (OR1) ₄ or R2Si (OR3) ₃ or a mixture thereof can be used as the alkoxysilane. Here, R1 and R3 are CH ₃ group, C ₃ H ₅ group, and C ₂ H ₄ represents a hydrolyzable group such as OCH ₃ group, R2 represents an organic functional group.

  In addition, since the metal oxide film obtained by hydrolyzing and condensing a metal alkoxide is hard, a crack is easily generated due to external force or strain due to volume reduction during condensation. Therefore, it is very difficult to form the metal oxide film with a uniform thickness without causing cracks.

  In contrast, a film formed using a coating solution containing a polymer, a metal alkoxide and / or a hydrolysis product thereof, and water is more flexible than a metal oxide film, and thus cracks are generated. It is hard to do. However, in this film, the metal oxide is not uniformly dispersed microscopically, and a high gas barrier property may not be obtained.

  When a water-soluble polymer is used as this polymer, the metal oxide is brought into the polymer during condensation by utilizing the strong hydrogen bond between the polymer hydroxyl group and the hydroxyl group of the hydrolyzate of the metal alkoxide. It can be uniformly dispersed. Therefore, a gas barrier property close to that of a metal oxide film can be achieved. Therefore, when such a gas barrier coating 115 is formed on the inorganic oxide layer 114, a much higher gas barrier property can be achieved as compared with the case where they are used alone.

  Since the gas barrier coating 115 obtained by using the coating liquid containing the above-described metal alkoxide and / or its hydrolysis product, a water-soluble resin having a hydroxyl group, and water forms hydrogen bonds, it is a harsh environment. May swell due to water intrusion and eventually dissolve. Therefore, even if the gas barrier coating 115 can achieve high gas barrier properties by laminating the inorganic oxide layer 114 and the gas barrier coating 115, the gas barrier coating 115 can adhere to and adhere to gas barrier properties under severe conditions such as a humid environment. Can easily deteriorate.

For example, when an alkoxysilane represented by the general formula R 2 Si (OR ₃ ) ₃ is used as the metal alkoxide, it is possible to obtain a gas barrier coating 115 that hardly swells even when water enters, that is, has excellent water resistance. In particular, when the organic functional group R2 is a water-insoluble functional group such as a vinyl group, an epoxy group, a methacryloxy group, a ureido group, and an isocyanate group, higher water resistance can be achieved.

The organic functional group R2 may be an isocyanurate group formed by polymerizing an isocyanate group. The alkoxysilane represented by the general formula R2Si (OR3) ₃ and having an isocyanurate group as the organic functional group R2 is obtained by polymerizing 3-isocyanatoalkylalkoxysilane to form a nurate, 3,5-tris (3-trialkoxysilylalkyl) isocyanurate. 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate does not have chemical reactivity in the isocyanurate part, but has chemical reactivity as if due to the polarity of the nurate part. It is known to behave as if In general, 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate is added to an adhesive or the like in the same manner as an isocyanate alkylalkoxysilane and is used as an adhesion improver. Therefore, a coating solution containing 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate, an alkoxysilane represented by the general formula Si (OR1) ₄ , a water-soluble polymer having a hydroxyl group, and water. By using this, it is difficult to cause swelling due to hydrogen bonding, and a gas barrier coating 115 having excellent water resistance can be obtained.

  Moreover, 3-isocyanate alkylalkoxysilane has high reactivity and low stability in an aqueous solution. On the other hand, 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate has a nurate part that is not water-soluble, but is easily dispersed in an aqueous liquid due to its polarity, and the liquid viscosity is stabilized Can keep. And 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate realizes water resistance equivalent to 3-isocyanate alkylalkoxysilane. In addition, the nurate part not only contributes to water resistance, but also suppresses the formation of gas barrier holes in the gas barrier coating 115 due to its polarity.

  1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate can be produced by thermal condensation of 3-isocyanatoalkylalkoxysilane. 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate may contain unreacted 3-isocyanatoalkylalkoxysilane.

  Examples of 1,3,5-tris (3-trialkoxysilylalkyl) isocyanurate include 1,3,5-tris (3) such as 1,3,5-tris (3-trimethoxysilylsilylpropyl) isocyanurate. -Trialkoxysilylpropyl) isocyanurate may be used. 1,3,5-tris (3-trialkoxysilylpropyl) isocyanurate is available at a relatively low cost. 1,3,5-tris (3-trialkoxysilylpropyl) isocyanurate is available at a relatively low cost and has a high hydrolysis rate.

When the metal alkoxide is an alkoxysilane represented by the general formula R2Si (OR3) ₃ and the organic functional group R2 is a vinyl group or a methacryloxy group, irradiation with ionizing radiation such as ultraviolet rays and electron beams is necessary in the production process. Therefore, facilities and manufacturing costs tend to be high. The alkoxysilane whose organic functional group R2 is a ureido group has a characteristic odor. The alkoxysilane in which the organic functional group R2 is an isocyanate group has a short pot life and is inferior in terms of handling properties as compared with other alkoxysilanes. From the above viewpoint, the alkoxysilane in which the organic functional group R2 is an isocyanurate group is superior to other alkoxysilanes.

When a mixture of an alkoxysilane represented by the general formula Si (OR1) ₄ and an alkoxysilane represented by the general formula R2Si (OR3) ₃ is used as the metal alkoxide, the ratio of these alkoxysilanes is, for example, R2Si (OR3 ) and in the range ₃ ratio of R2Si (OH) ₃ in terms of mass and Si (OR1) ₄ of R2Si to the sum of the terms of SiO ₂ by weight (oR @ 3) ₃ R2Si (OH) ₃ reduced mass of 1% to 50% You may set so that. When this ratio is reduced, the water resistance is lowered. Further, when this ratio is increased, the organic functional group R2 becomes a pore of the gas barrier, and the gas barrier property is lowered.

The mixing ratio of the alkoxysilane represented by the general formula Si (OR1) ₄ and the alkoxysilane represented by the general formula R2Si (OR3) ₃ is set so that the above ratio is in the range of 5 to 30%. May be. In this case, sufficient water resistance and high barrier properties can be achieved for long-term storage of liquid contents or moisture-containing contents in a humid environment.

When the SiO ₂ equivalent mass of Si (OR1) ₄ is M ₁ , the R2Si (OH) ₃ equivalent mass of R2Si (OR3) ₃ is M _2, and the mass of the water-soluble polymer is M ₃ , the ratio M ₁ / (M ₂ / M ₃ ) may be set within a range of 100/100 to 100/30, for example. In this case, in addition to obtaining a barrier property sufficient for long-term storage and boiling treatment, a gas barrier coating 115 having excellent flexibility can be obtained. Therefore, it is advantageous in obtaining the packaging material 10 having excellent flexibility.

Of the alkoxysilanes represented by the general formula Si (OR1) ₄ , tetraethoxysilane has a hydrolyzate that can exist relatively stably in an aqueous solvent. Therefore, when this is used, control of manufacturing conditions is relatively easy.

When tetraethoxysilane is used as the metal alkoxide and PVA is used as the water-soluble polymer, the ratio of the tetraethoxysilane SiO ₂ equivalent mass to the mass of the water-soluble polymer is, for example, 100/10 to 100 / Within the range of 100. When this ratio is increased, the gas barrier coating 115 is hardened and is likely to be cracked. Further, when this ratio is reduced, the water resistance is lowered.

When a mixture of an alkoxysilane represented by the general formula Si (OR1) ₄ and an alkoxysilane represented by the general formula R2Si (OR3) ₃ is used as the metal alkoxide, how are these alkoxides and water-soluble polymers? They may be mixed in any order. For example, an alkoxysilane represented by the general formula Si (OR1) ₄ and an alkoxysilane represented by the general formula R2Si (OR3) ₃ are separately hydrolyzed, and then these are contained in a solution containing a water-soluble polymer. May be added. This method is excellent in terms of dispersibility of silicon oxide and efficiency of hydrolysis.

  The coating liquid for forming the gas barrier film 115 includes an improvement in wettability of the gas barrier film 115 with respect to the ink or the adhesive, an improvement in adhesion between the gas barrier film 115 and the ink layer or the adhesive layer, An additive may be added in consideration of prevention of cracking due to shrinkage. As this additive, for example, clay minerals such as isocyanate compounds, colloidal silica, smectite, stabilizers, colorants, rheology modifiers, and mixtures thereof can be used.

  When the gas barrier film 115 is thin, it is difficult to form the gas barrier film 115 as a continuous film having a uniform thickness, and sufficient gas barrier properties cannot be obtained. The thick gas barrier coating 115 is liable to crack. The thickness of the gas barrier coating 115 is, for example, in the range of 0.01 μm to 50 μm.

  The coating liquid for forming the gas barrier coating 115 is, 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 It can apply | coat by the gravure offset method. The coating film formed by applying this coating liquid can be dried by, for example, a hot air drying method, a hot roll drying method, a high frequency irradiation method, an infrared irradiation method, an ultraviolet irradiation method, or a combination thereof.

  The adhesive layer 12 is a transparent layer coated with a gas barrier coating 115. Examples of the material of the adhesive layer 12 include polyurethane, polyester urethane, polyester, polyamide, epoxy resin, polyacrylic acid, polymethacrylic acid, polyethyleneimine, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, Solvent-free, solvent-type, aqueous-type, or hot-melt-type adhesives containing polyvinyl acetate, polyolefin, modified polyolefin, polybutadiene, wax, casein, or a mixture thereof as a main component can be used.

For applying the adhesive onto the gas barrier coating 115, for example, a direct gravure coating method, a reverse gravure coating method, a kiss coating method, a die coating method, a roll coating method, a dip coating method, a knife coating method, a spray coating method, or The Fontencourt method can be used. For example, the adhesive is applied in a dry state so that the application amount is within a range of 0.1 g / m ^{2 to} 8 g / m ² .

  The heat-sealable resin layer 13 is a transparent layer bonded to the transparent gas barrier film 11 via the adhesive layer 12. The heat-sealable resin layer 13 faces the substrate film 111 with the easy-adhesion layer 112, the inorganic oxide layer 114, the gas barrier film 115, and the adhesive layer 12 interposed therebetween.

  The heat sealable resin layer 13 is a transparent resin layer having heat sealability. Examples of the material of the heat-sealable resin layer 13 include polyethylene such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, polyester, polyamide, and ethylene. -Vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, polycarbonate, polyacrylonitrile, nitrocellulose, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, Biodegradable resins such as ethylene-methacrylic acid ester copolymers, cross-linked products of these, or polylactic acid resins can be used.

  The thickness of the heat-sealable resin layer 13 is set according to the application of the transparent packaging material 10, for example. Usually, the thickness of the heat-sealable resin layer 13 is in the range of 10 μm to 200 μm.

  For bonding the heat-sealable resin layer 13 and the transparent gas barrier film 11, for example, a dry lamination method, a non-solvent lamination method, or an extrusion lamination method can be used. For example, when the extrusion laminating method is used, the adhesive layer 12 can be omitted.

  A layer other than the adhesive layer 12 may be interposed between the transparent gas barrier film 11 and the heat sealable resin layer 13. For example, a printing layer and / or a base film may be interposed between them.

  This transparent packaging material 10 can be used as at least a part of a package. For example, a bag can be formed using this transparent packaging material 10. Alternatively, the transparent packaging material 10 can be used to form a lid of a molded container. The heat-sealable resin layer 13 is positioned between the internal space of the package and the transparent gas barrier film 11.

  This transparent packaging material 10 is excellent in adhesion between the plastic substrate film 111 and the heat-sealable resin layer 13. Therefore, for example, even when the liquid-containing contents are packaged with the transparent packaging material 10, the adhesion between the films hardly decreases, and therefore delamination hardly occurs. In addition, a packaged product obtained by packaging food or the like with this transparent packaging material 10 is less likely to cause delamination even when subjected to boiling sterilization treatment. Further, the packaged product obtained by wrapping the content containing the flavor component with the transparent packaging material 10 is an adhesive property between the plastic substrate film 111 and the heat-sealable resin layer 13 even when stored for a long period of time. Will not drop significantly. In addition, the packaged product in which precision electronic components and the like are packaged with the transparent packaging material 10 has a plastic substrate film 111 and a heat-sealable resin layer 13 even when left in a high temperature and high humidity environment for a long time. There is no significant decrease in adhesion. Therefore, deterioration of the contents can be prevented over a long period of time.

  This transparent packaging material 10 is excellent in wet laminate strength. Therefore, the transparent packaging material 10 has a wet laminate strength of, for example, 2.0 N / 15 mm or more when water is immersed in the interface between the transparent gas barrier film 11 and the heat sealable resin layer 13.

Moreover, this transparent packaging material 10 is excellent in normal laminate strength. Therefore, the package product formed by filling the four-sided seal bag formed using this transparent packaging material with water as the contents is subjected to the boiling treatment at 95 ° C. for 30 minutes, and the transparent gas barrier film 11 and the heat seal. The normal laminate strength with the conductive resin layer 13 is maintained at, for example, 3.0 N / 15 mm or more, and the transparent packaging material 10 maintains the oxygen permeability at, for example, 50 cm ³ / m ² · day · MPa or less. The packaged product formed by filling the four-side sealed bag formed using the transparent packaging material 10 with water as the contents is left for 3 months in an environment where the temperature is 40 ° C. and the relative humidity is 90%. After that, the normal laminate strength of the transparent gas barrier film 11 and the heat sealable resin layer 13 is maintained at, for example, 3.0 N / 15 mm or more, and the transparent packaging material 10 has an oxygen permeability of, for example, 20 cm ³ / m ^2. The pressure is kept below day · MPa.

Examples of the present invention will be described below.
<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 liquid A1”.

<Preparation of coating liquid A2>
An aqueous solution containing a water-dispersible polyester polyurethane polyurea resin containing adipic acid as a dibasic acid component of polyester and bisphenol A glycidyl ether in a mass ratio of 100: 5 was prepared. Hereinafter, this aqueous solution is referred to as “coating liquid A2.”

<Preparation of coating liquid A3>
An aqueous solution containing a water-dispersible polyester polyurethane having adipic acid as a dibasic acid component of polyester was prepared. That is, an aqueous solution having the same composition as the coating liquid A1 was prepared except that bisphenol A glycidyl ether was omitted. Hereinafter, this aqueous solution is referred to as “coating liquid A3”.

<Preparation of coating liquid A4>
An aqueous solution containing a water-dispersible polyester containing phthalic acid as a dibasic acid component of polyester and bisphenol A glycidyl ether in a solid content mass ratio of 100: 6 was prepared. That is, an aqueous solution having the same composition as the coating liquid A1 was prepared except that the dibasic acid component of the polyester was phthalic acid instead of adipic acid. Hereinafter, this aqueous solution is referred to as “coating liquid A4”.

<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 30 mg KOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.6 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 B2”.

<Preparation of coating solution B3>
A 6 g acrylic polyol solution containing an acrylic polyol having a hydroxyl value of 340 mg KOH / g at a concentration of 50% by mass was prepared. This acrylic polyol solution and 0.6 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 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 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 0.75 g of xylylene diisocyanate. 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 20% 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 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. 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 R2Si (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 R2Si (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-glycidoxypropyltrimethoxysilane. The mass ratio of water to isopropyl alcohol was 50:50. The concentration of γ-glycidoxypropyltrimethoxysilane in this mixed solution was 5% by mass in terms of R2Si (OH) ₃ . The mixture was then stirred for 30 minutes to cause hydrolysis of γ-glycidoxypropyltrimethoxysilane. As a result, a hydrolyzed solution containing a solid content of 5% by mass in terms of R2Si (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 were mixed so that the mass ratio of the solid content was 70:20:10. Hereinafter, this liquid mixture is referred to as “coating liquid C3”.

<Preparation of coating liquid C4>
The solution S1, the solution S2, and the solution S3 were mixed so that the mass ratio of their solid contents was 30:20:60. Hereinafter, this liquid mixture is referred to as “coating liquid C4”.

<Preparation of coating liquid C5>
The solution S1, the solution S2, and the solution S4 were mixed so that the mass ratio of their solid contents was 80:10:10. Hereinafter, this liquid mixture is referred to as “coating liquid C5”.

<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>
First, an unstretched substrate film made of nylon 6 and having a thickness of 150 μm was formed by a T-die method. Next, this base film was passed through heating rollers having different peripheral speeds and longitudinally stretched 3.0 times.

  Next, the coating liquid A1 was applied on one main surface of the base film by the Meyer bar coating method. Then, the coating film was dried in the preheating part, and the base film was then stretched 3.3 times in the transverse direction. Furthermore, the heat setting process was performed at the temperature of 215 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 0.08 μm was obtained.
Further, an inorganic oxide layer and a gas barrier film were sequentially formed by the same method as described for the transparent gas barrier film BF1.

  As described above, a transparent gas barrier film was completed. 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>
A transparent gas barrier film is produced in the same manner as described for the transparent gas barrier film BF1 except that the coating liquid A2 is used instead of the coating liquid A1 and the thickness of the easy adhesion layer is 0.10 μm. did. 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>
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 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>
A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film BF1 except that the thickness of the easy adhesion layer was 0.30 μm. 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>
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 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>
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 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>
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 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>
Transparent gas barrier film BF1 except that instead of forming an anchor coat layer having a thickness of 0.05 μm using coating liquid B1, an anchor coat layer having a thickness of 1.0 μm was formed using coating liquid B4. A transparent gas barrier film was produced by the same method as described above. That is, a transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF8 except that the thickness of the anchor coat layer was 1.0 μm. 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 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 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>
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 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>
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 C4. 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 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>
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 C5. 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 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>
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 BF10 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 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”.

<Manufacture of transparent gas barrier film BF15 and transparent packaging material PM15>
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 BF10 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 BF15”.

  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 BF15 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM15”.

<Manufacture of transparent gas barrier film BF16 and transparent packaging material PM16>
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 BF10 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 BF16”.

  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 BF16 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM16”.

<Manufacture of transparent gas barrier film BF17 and transparent packaging material PM17>
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. Except for forming an oxide layer and forming a gas barrier film having a thickness of 0.5 μm using the coating liquid C2 instead of forming a gas barrier film having a thickness of 0.3 μm using the coating liquid C1. A transparent gas barrier film was produced by the same method as described for the transparent gas barrier film BF1. 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 BF10 except that the inorganic oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF17”.

  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 BF17 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM17”.

<Manufacture of transparent gas barrier film BF18 and transparent packaging material PM18>
Instead of forming an inorganic oxide layer made of aluminum oxide by a vacuum vapor deposition device using an electron beam heating method, an inorganic oxide layer made of magnesium oxide is formed by a vacuum vapor deposition device using an electron beam heating method, and a coating solution The transparent gas barrier film BF1 was described except that a gas barrier film having a thickness of 0.5 μm was formed using the coating liquid C2 instead of forming a gas barrier film having a thickness of 0.3 μm using C1. A transparent gas barrier film was produced by the same method as described above. That is, instead of forming an inorganic oxide layer made of aluminum oxide by a vacuum vapor deposition device using an electron beam heating method, an inorganic oxide layer made of magnesium oxide was formed by a vacuum vapor deposition device using an electron beam heating method. Except for the above, a transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film BF10. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF18”.

  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 BF18 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM18”.

<Manufacture of transparent gas barrier film BF19 and transparent packaging material PM19>
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 A3 was used instead of the coating liquid A1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF19”.

  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 BF19 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM19”.

<Manufacture of transparent gas barrier film BF20 and transparent packaging material PM20>
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 A4 was used instead of the coating liquid A1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film BF20”.

  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 BF20 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM20”.

<Manufacture of transparent gas barrier film BF21 and transparent packaging material PM21>
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 BF21”.

  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 BF21 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM21”.

<Manufacture of transparent gas barrier film BF22 and transparent packaging material PM22>
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 BF22”.

  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 BF22 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM22”.

<Manufacture of transparent gas barrier film BF23 and transparent packaging material PM23>
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 BF23”.

  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 BF23 was used instead of the transparent gas barrier film BF1. Hereinafter, this transparent packaging material is referred to as “transparent packaging material PM23”.

<TOF-SIMS analysis of easy adhesion layer>
Each easy adhesion layer of the transparent gas barrier films BF1 to BF23 was analyzed by TOF-SIMS. In addition, about the transparent gas barrier film BF21, since the easily bonding layer was not provided, the analysis by TOF-SIMS was not performed here.

As the TOF-SIMS analyzer, TRIFT2 manufactured by ULVAC-PHI was used. ⁶⁹ Ga ⁺ was used as the primary ion, and the primary ion acceleration voltage was 15 kV. The measurement area was 150 μm square, and the measurement time was 3 minutes. The measurement was carried out using a charge correcting electron gun, and the ion species from the easy-adhesion layer were analyzed by positive and negative secondary ion mass spectra.

  As a result, it was determined that a nitrogen atom-containing component, an adipic acid component, and a bisphenol glycidyl ether component were present in each easy-adhesion layer of the transparent gas barrier films BF1 to BF18 and BF22 to BF23. On the other hand, regarding the easy adhesion layer of the transparent gas barrier film BF19, it was determined that a nitrogen atom-containing component and an adipic acid component were present, but a bisphenol glycidyl ether component was not detected. Furthermore, although it was judged that the nitrogen atom-containing component and the bisphenol glycidyl ether component were present in the easy adhesion layer of the transparent gas barrier film BF20, the adipic acid component was not detected.

  For each of the easy-adhesion layers of the transparent gas barrier films BF1 to BF18 and BF22 to BF23, main peaks confirmed by positive and negative secondary ion mass spectrum analysis by TOF-SIMS were as follows.

(1) Peak derived from nitrogen atom-containing component: CNO ⁻
(2) Peak groups derived from the adipic acid component: C ₆ H ₇ O ₂ ⁻ , C ₆ H ₉ O ₃ ⁻
(3) Peak group derived from bisphenol glycidyl ether component: C ₉ H ₁₁ O ⁺ , C ₁₄ H ₁₃ O ₂ ⁺ , C ₁₄ H ₁₁ O ₂ ⁻
<TOF-SIMS analysis of anchor coat layer>
Positive and negative secondary ion mass spectrum analysis by TOF-SIMS was performed on each anchor coat layer of the transparent gas barrier films BF1 to BF23. In addition, about transparent gas barrier film BF22, since the anchor coat layer was not provided, the analysis by TOF-SIMS was not performed. Measurement was performed in the same manner as that performed for the easy-adhesion layer, and the positive and negative secondary ion mass spectra obtained thereby were used to analyze the ion species from the anchor coat layer.

  It was determined that an aromatic hydrocarbon component, a nitrogen atom-containing component, a methacrylate component, and a silane compound component were present in each anchor coat layer of the transparent gas barrier films BF1 to BF21. On the other hand, regarding the anchor coat layer of the transparent gas barrier film BF23, it was determined that the aromatic hydrocarbon component, the nitrogen atom-containing component, and the silane compound component were present, but the methacrylate component was not detected. .

  For each anchor coat layer of the transparent gas barrier films BF1 to BF21, main peaks confirmed by positive and negative secondary ion mass spectral analysis by TOF-SIMS were as follows.

(1) Peak groups derived from aromatic hydrocarbon components: C ₇ H ₇ ⁺ , C ₈ H ₉ ⁺ , C ₉ H ₇ ⁺ , C ₁₀ H ₉ ⁺
(2) Peak groups derived from nitrogen atom-containing components: CN ⁻ , CNO ⁻
(3) methacrylate component derived ^{_{peaks: C 4 H 5 O +,}} C 4 H 5 O 2 -
(4) Peak groups derived from silane compound components: C ₂ H ₇ O ₂ Si ⁺ , C ₃ H ₉ O ₃ Si ⁺
<Measurement of oxygen permeability>
About each of transparent gas barrier film BF1 thru | or BF23, the oxygen permeability was measured according to the B method (isobaric method) prescribed | regulated by Japanese Industrial Standards JISK7126-1987 "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.

<Measurement of wet laminate strength>
For each of the transparent packaging materials PM1 to PM23, according to the test method specified in Japanese Industrial Standards JIS K6854-3: 1999 "Adhesive-Peeling adhesive strength test method-Part 3: T-peeling" It was measured.

  That is, first, a strip-shaped test piece having a width of 15 mm was prepared from each of the transparent packaging materials PM1 to PM23. 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. Then, 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 (gripping distance) and the tensile stress. Was recorded. 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.

<Measurement of oxygen permeability after boiling treatment>
Using each of the transparent packaging materials PM1 to PM23, 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. Tables 2 and 3 below summarize the measurement results.

<Measurement of normal laminate strength after boiling>
Using each of the transparent packaging materials PM1 to PM23, 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 boiling treatment at 95 ° C. for 30 minutes, and then the normal laminate strength was measured.

  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. Tables 2 and 3 below summarize the measurement results.

<Measurement of normal laminate strength after storage of contents>
Using each of the transparent packaging materials PM1 to PM23, 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. These packages were left for 3 months in an environment having a temperature of 40 ° C. and a relative humidity of 90%.

  Thereafter, for the transparent packaging materials PM1 to PM23 used in these packaging products, the test specified in Japanese Industrial Standards JIS K6854-3: 1999 “Adhesive-Peeling adhesive strength test method-Part 3: T-type peeling”. The normal laminate strength was measured according to the method. 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. Tables 2 and 3 below summarize the measurement results.

<Drop test>
Ten transparent packaging materials having a size of 100 mm × 150 mm were prepared for each of the transparent packaging materials PM1 to PM23. Each four-sided seal bag was filled with 150 g of water. These packages were left for 3 months in an environment having a temperature of 40 ° C. and a relative humidity of 90%.

Next, each of these packaged products was left in an environment having a temperature of 5 ° C. for 3 days, and then dropped 50 times from a height of 1.5 m. Then, for each of the transparent packaging materials PM1 to PM23, the number of bags torn by this drop test was determined. Tables 2 and 3 below summarize the test results.

  As shown in Tables 1 to 3, the transparent packaging materials PM19 to PM23 had low wet laminate strength and normal laminate strength after boiling and storage of contents. And transparent packaging materials PM19 thru | or PM23 have remarkably low gas-barrier property after a boiling process and the content preservation | save, and the packaging body manufactured using these is partly or all in the drop test after the content preservation | save. Damaged.

On the other hand, the transparent packaging materials PM1 to 18 had higher wet laminate strength and normal laminate strength after boiling treatment and storage of the contents than the transparent packaging materials PM19 to PM23. And transparent packaging material PM1 thru | or 18 has the gas barrier property after boiling processing and the preservation | save of a content high enough, and the package manufactured using these produces a failure | damage by the drop test after a preservation | save of contents. There was no.
The invention described in the original claims is appended below.
[1] a base film made of polyamide resin;
Formed on one main surface of the base film, an easy adhesion layer containing nitrogen atoms, adipic acid and bisphenol glycidyl ether;
An anchor coat layer formed on the easy-adhesion layer and containing a reaction product of a composition containing a polyol and an isocyanate compound;
A transparent gas barrier film comprising an inorganic oxide layer formed on the easy adhesion layer by a vapor deposition method.
[2] When the positive and negative secondary ion mass spectrum analysis of the easy-adhesion layer with a time-of-flight secondary ion mass spectrometer was performed, the results were as follows: nitrogen atom-containing component, adipic acid component, bisphenol glycidyl ether Item 2. The transparent gas barrier film according to Item 1, which exhibits the presence of a component.
[3] When positive and negative secondary ion mass spectrum analysis of the easy-adhesion layer using a time-of-flight secondary ion mass spectrometer is performed, a peak of CNO ⁻ as a peak derived from a nitrogen atom-containing component , and adipic acid C ₆ H ₇ O ₂ as peaks derived from the component ^- and C ₆ H ₉ O ₃ ^- and the peak of, C ₉ as a peak group derived from bisphenol glycidyl ether component _{^{H 11 O +, C 14 H}} 13 O 2 + and C ₁₄ H ₁₁ O ₂ ^- of the transparent gas barrier film according to claim 1, characterized in that the peak is detected.
[4] The gas barrier film according to any one of [1] to [3], wherein the easy-adhesion layer contains a water-dispersible polyester polyurethane or a water-dispersible polyester polyurethane polyurea resin.
[5] Any one of Items 1 to 4, wherein the easy-adhesion layer material is applied onto the non-stretched base film, and then the base film is simultaneously biaxially stretched. The gas barrier film according to 1.
[6] The material according to any one of Items 1 to 4, wherein the easy-adhesion layer material is applied on the base film uniaxially stretched in the longitudinal direction, and then the base film is stretched in the lateral direction. 2. The gas barrier film according to claim 1.
[7] The anchor coat layer according to any one of items 1 to 6, wherein the anchor coat layer includes a reaction product of an acrylic polyol, an isocyanate compound, a silane coupling agent, or a hydrolysis product thereof. Gas barrier film.
[8] The inorganic oxide layer is made of a material selected from the group consisting of aluminum oxide, silicon oxide, tin oxide, magnesium oxide, and a mixture containing two or more thereof. The gas barrier film according to any one of the above.
[9] The gas barrier property according to any one of items 1 to 8, further comprising a gas barrier film formed on the inorganic oxide layer and made of a mixture containing a transparent resin and an inorganic substance. the film.
[10] The gas barrier coating is formed by applying a solution containing a water-soluble polymer, a tetraalkoxysilane or a hydrolysis product thereof, and a trialkoxysilane or a hydrolysis product thereof on the inorganic oxide layer. Item 10. The gas barrier film according to Item 9, wherein the gas barrier film is formed by drying a coating film obtained by the method.
[11] The gas barrier film according to [10], wherein the organic functional group other than the alkoxy group bonded to silicon of the trialkoxysilane is a hydrophobic organic functional group.
[12] The gas barrier coating comprises a solution containing water, a water-soluble polymer, at least one compound selected from the group consisting of a metal alkoxide, a hydrolysis product thereof, and tin chloride. Item 10. The gas barrier film according to Item 9, wherein the gas barrier film is formed by applying on a physical layer and drying a coating film obtained thereby.
[13] The heat-sealing resin bonded to the gas barrier film according to any one of items 1 to 12 and the base film with the inorganic oxide layer sandwiched between the gas barrier film and the gas barrier film. A transparent packaging material comprising a layer.
[14] A package comprising the packaging material according to item 13.

Sectional drawing which shows schematically the transparent packaging material which concerns on 1 aspect 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 coating.

Claims (12)

A base film made of polyamide resin;
Formed on one main surface of the base film, an easy adhesion layer containing nitrogen atoms, adipic acid and bisphenol glycidyl ether;
An anchor coat layer formed on the easy-adhesion layer and containing a reaction product of a composition containing a polyol and an isocyanate compound;
An inorganic oxide layer formed on the anchor coat layer by a vapor deposition method, and performing positive and negative secondary ion mass spectrum analysis of the easy-adhesion layer using a time-of-flight secondary ion mass spectrometer. CNO ⁻ peak as a peak derived from a nitrogen atom-containing component , C ₆ H ₇ O ₂ ⁻ and C ₆ H ₉ O ₃ ⁻ peaks as a peak group derived from an adipic acid component, and a bisphenol glycidyl ether component transparent gas barrier film that of the peak, characterized in that is detected ^- C ₉ H ₁₁ O ⁺ as a peak group, C ₁₄ H ₁₃ O ₂ ⁺ and C ₁₄ H ₁₁ O _2. The gas barrier film according to claim 1, wherein the easy adhesion layer contains a water-dispersible polyester polyurethane or a water-dispersible polyester polyurethane polyurea resin. The gas barrier film according to claim 1 or 2 , wherein the material for the easy-adhesion layer is applied onto the non-stretched base film, and then the base film is simultaneously biaxially stretched. The gas barrier according to claim 1 or 2 , wherein the easy-adhesion layer material is applied onto the base film that has been uniaxially stretched in the longitudinal direction, and then the base film is stretched in the transverse direction. Sex film. The gas barrier property according to any one of claims 1 to 4 , wherein the anchor coat layer includes a reaction product of an acrylic polyol, an isocyanate compound, a silane coupling agent, or a hydrolysis product thereof. the film. The inorganic oxide layer include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, and any of claims 1 to 5, characterized in that it consists of a material selected from the group consisting of a mixture containing two or more of them 2. The gas barrier film according to claim 1. The gas barrier film according to any one of claims 1 to 6 , further comprising a gas barrier film formed on the inorganic oxide layer and made of a mixture containing a transparent resin and an inorganic substance. The gas barrier coating is obtained by applying a solution containing a water-soluble polymer, a tetraalkoxysilane or a hydrolysis product thereof, and a trialkoxysilane or a hydrolysis product thereof on the inorganic oxide layer. The gas barrier film according to claim 7 , wherein the gas barrier film is formed by drying the coated film. The gas barrier film according to claim 8 , 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 7 , wherein the gas barrier film is formed by applying to a substrate and drying the coating film obtained thereby. A gas barrier film according to any one of claims 1 to 10 , and a heat-sealable resin layer bonded to the gas barrier film and facing the base film with the inorganic oxide layer interposed therebetween A transparent packaging material characterized by comprising: A package comprising the packaging material according to claim 11 .

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