JP2010018302A - Transparent gas barrier film, and transparent packaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film capable of ensuring the gas barrier properties without increasing the thickness of an inorganic oxide layer in a transparent gas barrier film in which an anchor coat layer and the inorganic oxide layer are successively formed on at least one surface of a base material film, and a transparent packaging material using the same. <P>SOLUTION: In the transparent gas barrier film, the ratio of the number of unevenness exceeding ±1.5 nm from the mean line of a roughness curve in an interface between the anchor coat layer and the inorganic oxide layer to the entire unevenness number is ≤12%, the standard deviation of the height of the entire unevenness from the mean line of the roughness curve in the interface is <1.0, and the standard deviation of the height of the entire unevenness from the mean line in the roughness curve of the interface is <1.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a transparent gas barrier film excellent in gas barrier properties, which is formed by sequentially forming an anchor coat layer and an inorganic oxide layer on at least one surface of a base film, and a transparent packaging material using the same.

  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. Moreover, when pharmaceuticals are packaged with high gas barrier packaging materials, alteration and dissipation of active ingredients can be prevented, and when electronic parts are packaged with high gas barrier packaging materials, metal corrosion and insulation failure 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.

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

  For example, a high gas barrier packaging material including an EVOH layer or a 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 properties are significantly deteriorated.

  Patent Documents 1 and 2 disclose a gas barrier film in which an inorganic oxide layer made of silicon oxide, aluminum oxide, or magnesium oxide is formed on a plastic substrate film by a vapor deposition method such as vacuum evaporation or sputtering. Are listed. 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, as one of the problems when forming a gas barrier film by forming an inorganic oxide layer on a plastic substrate film by vapor deposition, the problem of smoothness of the surface on which the inorganic oxide layer is formed has been pointed out. ing. In general, fine irregularities exist on the plastic substrate film, and when an inorganic oxide layer is formed on the plastic substrate film by a vapor deposition method, defects resulting from the formation on the fine irregularities Has been pointed out in the inorganic oxide layer, which deteriorates the gas barrier property. In order to improve the adhesion between the plastic base film and the inorganic oxide layer, an anchor coat layer is formed between the plastic base film and the inorganic oxide layer. The smoothness of the coated surface of the anchor coat layer is important.

In view of such a situation, various improvements have been made to improve the gas barrier properties of a gas barrier film formed by laminating inorganic oxide layers formed by a vapor deposition method. For example, when an anchor coat is applied to a plastic film and the roughness of the anchor coat layer surface is specified (Patent Documents 3, 4, 5, etc.), the roughness of the surface of the plastic substrate on which the inorganic oxide thin film is laminated Proposed (Patent Documents 6, 7, 8, etc.), those defining the surface roughness of the inorganic oxide thin film layer (Patent Document 9, etc.), etc. have been proposed.
U.S. Pat. No. 3,442,686 JP 49-041469 A JP-A-11-216828 JP-A-10-244601 Japanese Patent No. 4014931 Japanese Patent No. 3935598 JP 2001-310412 A JP 2002-321301 A Japanese Patent No. 3675904

  However, even in the film that has been improved, the gas barrier performance of the gas barrier film is not always sufficient, so that it is necessary to increase the thickness of the inorganic oxide layer. When the thickness of the inorganic oxide layer is increased, there is a problem that practicality as a packaging material is reduced due to generation of cracks in the thin film, decrease in adhesion, decrease in transparency, curl of the film, and increase in cost.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the interface after the inorganic oxide layer is formed, that is, the surface roughness of the interface between the anchor coat layer and the inorganic oxide layer on the base film. Has been found to have various influences in order to develop excellent gas barrier performance, and the present invention has been completed.
The invention according to claim 1 of the present invention is a transparent gas barrier property in which an anchor coat layer is formed on at least one surface of a base film, and an inorganic oxide layer formed by a vapor deposition method is further formed on the anchor coat layer. In the film, a continuous tilted TEM image (−60 ° to + 60 °, 1 ° step) was taken at the interface between the anchor coat layer and the inorganic oxide layer, and then image position correction was performed by the Fiducial Marker method. Regarding the roughness curve at the interface when the dimensional reconstruction image was obtained, the ratio of the number of irregularities exceeding the height of 1.5 nm from the average line to the total number of irregularities is 12% or less, and The transparent gas barrier film is characterized in that the standard deviation of the heights of all the irregularities from the average line in the roughness curve is less than 1.0.

  The invention according to claim 2 of the present invention is characterized in that the inorganic oxide layer is made of a material selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide, tin oxide, and a mixture containing two or more thereof. The transparent gas barrier film according to claim 1.

  The invention according to claim 3 of the present invention is the transparent gas barrier film according to claim 1 or 2, wherein the substrate film is a plastic film.

The invention of claim 4 of the present invention is characterized in that a gas barrier coating layer formed on the inorganic oxide layer and made of a mixture containing a transparent resin and an inorganic substance is further laminated. It is a transparent gas barrier film given in any 1 paragraph.

  According to a fifth aspect of the present invention, the gas barrier coating layer comprises a solution containing a water-soluble polymer, a tetraalkoxysilane or a hydrolysis product thereof, and a trialkoxysilane or a hydrolysis product thereof. The transparent gas barrier film according to claim 4, wherein the transparent gas barrier film is formed by applying on a physical layer and drying a coating film obtained thereby.

  The invention according to claim 6 of the present invention is the transparent gas barrier film according to claim 5, wherein the organic functional group other than the alkoxy group bonded to silicon of the trialkoxysilane is a hydrophobic organic functional group. .

  The invention of claim 7 of the present invention is such that the gas barrier coating layer comprises at least one compound selected from the group consisting of water, a water-soluble polymer, a metal alkoxide, a hydrolysis product thereof, and tin chloride. The transparent gas barrier film according to claim 6, wherein the transparent gas barrier film is formed by applying a solution containing a solution on the inorganic oxide layer and drying a coating film obtained thereby.

  The invention of claim 8 of the present invention comprises the transparent gas barrier film, and a heat-sealable resin layer that is bonded to the transparent gas barrier film and faces the base film with the inorganic oxide layer interposed therebetween. It is the transparent packaging material characterized by having performed.

  According to the present invention, in the transparent gas barrier film in which the anchor coat layer and the inorganic oxide layer are sequentially formed on the base film, the surface of the interface between the anchor coat layer and the inorganic oxide layer after the inorganic oxide layer is formed. Since the roughness is defined within a specific range, it is possible to exhibit excellent gas barrier performance.

  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 20 includes a transparent gas barrier film 10, an adhesive layer 11, and a heat sealable resin layer 12.

  The transparent gas barrier film 10 includes a base film 1, an anchor coat layer 2, an inorganic oxide layer 3, and a gas barrier coating layer 4. 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 10 may be a known plastic as long as it is a transparent film, and may be stretched or unstretched, and preferably has mechanical strength and dimensional stability. The For example, polyester resins such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 12, metaxylenediamine-6 nylon (MXD6 nylon), polyamide resins such as copolymer nylon, polyvinyl alcohol resin, ethylene Examples thereof include polyvinyl alcohol resins such as vinyl alcohol copolymers, polyimide resins, polyetherimide resins, polysulfone resins, polyether sulfone resins, polyether ketone resins, polycarbonate resins, polyvinyl butyral resins, and mixtures thereof.

   Although there is no restriction | limiting in the thickness of the base film 1, The base film 1 needs to have the thickness which can achieve sufficient intensity | strength as a base material for laminating | stacking an inorganic oxide layer. Moreover, when the base film 1 is thick, the flexibility of the transparent packaging material 20 and the transparent gas barrier film 10 may be insufficient. The thickness of the base film 1 is, for example, in the range of 5 μm to 100 μm. In addition, the base film 1 is formed by in-line coating by applying a coating liquid on at least one surface of the base film 1 during the film forming process of the base film 1 and drying the coating film. You may use the base film 1 in which the easily bonding coat layer was formed.

  The coating liquid is not particularly limited as long as it has good adhesion to the anchor coat layer 2 laminated on the base film 1, for example, a water-dispersible polyester polyurethane containing adipic acid as a dibasic acid of polyester, The prepolymer, a water-dispersible polyester polyurethane polyurea resin containing adipic acid as a dibasic acid of polyester, the prepolymer, or a mixture containing two or more thereof as a main component, and the main chain or terminal of these polymers Examples thereof include those having a hydroxyl group, a carboxy group, or an amino group introduced therein, and coating liquids mainly composed of polyester urethane prepared from aromatic carboxylic acid, aliphatic carboxylic acid, polyol and isocyanate. In addition to the components described above, the coating liquid may further contain an additive.

  As this additive, for example, an antistatic agent, a lubricant, an antifoaming agent, and a surfactant can be used. Moreover, as a coating method at the time of forming the base film 1 of the coating liquid, for example, a gravure roll method, a reverse gravure coating method, a roll coating method, an air knife method, a Meyer bar coating method, or an inverse roll method is used. be able to.

  The anchor coat layer 2 is a transparent layer formed on the base film 1. The anchor coat layer 2 is a layer formed for improving the adhesion between the base film 1 and the inorganic oxide layer 3, and is not particularly limited as long as a material showing a strong adhesion is used for both. The anchor coat layer 2 preferably has heat resistance in order to maintain a smooth surface property when the inorganic oxide layer 3 is formed by a vapor deposition method. As such an example, a reaction product of a composition containing a polyol and an isocyanate compound can be exemplified. More specifically, 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, thereby increasing the cohesive strength of the anchor coat layer 2. Increase. Moreover, the alkoxy group of this silane coupling agent or the silanol group produced by the hydrolysis thereof strongly interacts with polar groups such as a metal contained in the inorganic oxide layer 3 and a hydroxyl group existing on the surface of the inorganic oxide. This improves the adhesion between the anchor coat layer 2 and the inorganic oxide layer 3.

  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 2 and the inorganic oxide layer 3, and acts mainly as a crosslinking agent or a curing agent. 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 2 is obtained, for example, by applying a coating liquid containing the above-described acrylic polyol, isocyanate compound, and silane coupling agent on the base film 1 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 base film 1. 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. When the coating liquid is applied and dried, the coating method and the drying method may be appropriately selected according to the coating liquid so that high smoothness can be obtained on the coated surface.

  Prior to application of the coating liquid, for example, in order to improve wettability and / or adhesion, the surface of the base film 1 is subjected to corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemicals, etc. A pretreatment by a conventionally known method such as a treatment may be performed.

  When the anchor coat layer 2 is thin, it is difficult to form the anchor coat layer 2 as a continuous film having a uniform thickness, and a smooth surface cannot be obtained, so that sufficient barrier properties and adhesion may not be obtained. . When the anchor coat layer 2 is thick, the flexibility is low, and cracking may occur when the transparent gas barrier film 10 is bent or pulled, which is not practical. The thickness of the anchor coat layer 2 is, for example, in the range of 0.005 μm to 1 μm, and typically in the range of 0.01 μm to 0.5 μm.

  The inorganic oxide layer 3 is a transparent layer having a gas barrier property formed on the anchor coat layer 2 by a vapor deposition method. As a material constituting the inorganic oxide layer 3, for example, silicon oxide, aluminum oxide, magnesium oxide, tin oxide, or a mixture thereof can be used.

  For the formation of the inorganic oxide layer 3, for example, a vacuum deposition 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 3 can be formed. In addition, when reactive vapor deposition in which a gas such as oxygen is blown during vapor deposition, the inorganic oxide layer 3 having excellent transparency can be formed.

  When the inorganic oxide layer 3 is thin, it is difficult to form the inorganic oxide layer 3 as a continuous film having a uniform thickness, and sufficient gas barrier properties cannot be obtained. The thick inorganic oxide layer 3 has low flexibility and may crack when the transparent gas barrier film 10 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 3 is, for example, in the range of 5 nm to 500 nm. After the inorganic oxide layer 3 is formed, a continuous inclined TEM image (−60 ° to + 60 °, 1 ° step) of the interface between the anchor coat layer 2 and the inorganic oxide layer 3 is taken, and then the Fiducial Marker method is used. Regarding the roughness curve at the interface when a three-dimensional reconstructed image is obtained by performing image position correction, the ratio of the number of irregularities exceeding ± 1.5 nm from the average line to the total number of irregularities is 12%. And the standard deviation of the height of all irregularities from the average line with respect to the roughness curve at the interface is less than 1.0.

  When the ratio of the number of irregularities exceeding ± 1.5 nm from the average line to the total number of irregularities exceeds 12%, the anchor coat layer / inorganic oxide layer interface roughness curve, If the standard deviation of the heights of all irregularities from the average line exceeds 1.0, the thin film layer of the inorganic oxide layer 3 cannot be smoothly laminated on the anchor coat layer 2, and a high gas barrier I can't get sex. In general, measurement of the surface roughness of the anchor coat layer 2 before forming the inorganic oxide layer 3 and measurement of the surface roughness of the inorganic oxide layer 3 after forming the inorganic oxide layer 3 are performed. However, the former does not represent an appropriate surface state when there is a possibility that the surface property of the anchor coat layer 2 may change after the inorganic oxide layer 3 is formed. In the latter, since the surface after the inorganic oxide layer 3 is deposited on the anchor coat layer 2 is observed, a difference is observed in the surface state depending on the laminated thickness.

  As described above, the conventional method for measuring the surface roughness has insufficient points for improving the gas barrier property and correlating the surface roughness, but the inorganic oxide layer 3 is formed on the anchor coat layer 2. There was no case where the roughness of the interface after the formation was analyzed and measured. In the present invention, as a result of diligent investigation paying attention to the surface roughness of the interface between the anchor coat layer 2 and the inorganic oxide layer 3, the roughness curve at the interface has irregularities exceeding ± 1.5 nm from the average line. The ratio of the number to the total number of irregularities is 12% or less, and the standard deviation of the height of all irregularities from the average line with respect to the roughness curve at the interface is less than 1.0. Can be improved.

  The gas barrier coating layer 4 is a transparent layer formed on the inorganic oxide layer 3. The gas barrier coating layer 4 is made of a mixture containing a transparent resin and an inorganic material such as an inorganic oxide. Although the gas barrier coating layer 4 can be omitted, the transparent packaging material 20 having higher gas barrier properties can be obtained by providing the gas barrier coating layer 4.

The gas barrier coating layer 4 is formed by, for example, 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 3 and heating the coating film. And dried. Alternatively, the gas barrier coating layer 4 is formed, for example, by applying a coating liquid containing a water-soluble polymer, tetraalkoxysilane or a hydrolysis product thereof, and trialkoxysilane or a hydrolysis product thereof on the inorganic oxide layer 3. It is obtained by applying and heating and drying the coating film. Alternatively, the gas barrier coating layer 4 is, for example, applied on the inorganic oxide layer 3 with a coating solution containing water and a water-soluble polymer and a metal alkoxide and / or a hydrolysis product thereof and tin chloride. It is obtained by heating and drying this 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 layer 4 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 represent hydrolyzable groups such as a CH ₃ group, a C ₃ H ₅ group, and a C ₂ H ₄ OCH ₃ group, and 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 layer 4 is formed on the inorganic oxide layer 3, a much higher gas barrier property can be achieved as compared with the case where they are used alone.

Since the gas barrier coating layer 4 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 severe. When used in the environment, it may swell due to the ingress of water, eventually resulting in dissolution. Therefore, even if this gas barrier coating layer 4 achieves a high gas barrier property by laminating the inorganic oxide layer 3 and the gas barrier coating layer 4, under severe conditions such as a humid environment, The gas barrier property may easily deteriorate.

For example, when an alkoxysilane represented by the general formula R2Si (OR3) ₃ is used as the metal alkoxide, it is difficult to swell even when water enters, that is, the gas barrier coating layer 4 having excellent water resistance can be obtained. . 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 the gas barrier coating layer 4 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 it is easily dispersed in an aqueous liquid due to its polarity, and the viscosity of the liquid 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 layer 4 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 in a hot and 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 sufficient barrier properties for long-term storage and boiling treatment, the gas barrier coating layer 4 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 layer 4 is hardened and easily 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 coating layer 4 includes improved wettability of the gas barrier coating layer 4 to ink or adhesive, improved adhesion between the gas barrier coating layer 4 and the ink layer or adhesive layer, and gas barrier properties. An additive may be added in consideration of prevention of generation of cracks due to shrinkage of the coating layer 4. 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 coating layer 4 is thin, it is difficult to form the gas barrier coating layer 4 as a continuous film having a uniform thickness, and sufficient gas barrier properties cannot be obtained. The thick gas barrier coating layer 4 tends to crack. The thickness of the gas barrier coating layer 4 is, for example, in the range of 0.01 μm to 10 μm.

  The coating liquid for forming the gas barrier coating layer 4 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 5 is a transparent layer coated with the gas barrier coating layer 4. Examples of the material for the adhesive layer 5 include polyurethane, polyester urethane, polyester, polycarbonate resin, polyamide, epoxy resin, polyacrylic acid, polymethacrylic acid, polyethyleneimine, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer. It is possible to use a solvent-free, solvent-based, water-based, or hot-melt type adhesive containing a polymer, polyvinyl acetate, polyolefin, modified polyolefin, polybutadiene, wax, casein, or a mixture thereof as a main component. it can.

In order to apply this adhesive onto the gas barrier coating layer 4, 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, Alternatively, the Fonten coating 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 6 is a transparent layer bonded to the transparent gas barrier film 10 via the adhesive layer 5. The heat-sealable resin layer 6 faces the base film 1 with the anchor coat 2, the inorganic oxide layer 3, the gas barrier coating layer 4 and the adhesive layer 5 interposed therebetween.

  The heat sealable resin layer 6 is a transparent resin layer having heat sealability. Examples of the material of the heat sealable resin layer 6 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. Alternatively, the above-described resin alone or a blend of two or more kinds may be used.

  The thickness of the heat-sealable resin layer 6 is set according to the use of the transparent packaging material 20, for example. Usually, the thickness of the heat-sealable resin layer 6 is in the range of 10 μm to 200 μm.

  For bonding the heat-sealable resin layer 6 and the transparent gas barrier film 10, 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 5 can be omitted.

  A layer other than the adhesive layer 5 may be interposed between the transparent gas barrier film 10 and the heat-sealable resin layer 6. For example, a printing layer and / or another base film may be interposed between them.

  Examples of the present invention will be described below. The evaluation methods of various physical properties of the transparent gas barrier film and the transparent packaging material shown in Examples and Comparative Examples are as follows. The evaluation results of these physical properties are summarized in Tables 1, 3, 5, and 7 for the transparent gas barrier film, and Tables 2, 4, 6, and 8 for the transparent packaging materials. .

<界面の凹凸比率、および凹凸の標準偏差>
透明バリアフィルムについて、ＦＩＢ−マイクロサンプリング法（装置 日立製ＦＢ−２１００、加速電圧 ４０ｋＶ）により断面薄膜試料（再構成用のマーカーとして金粒子を付着）を作成した。その後、連続傾斜ＴＥＭ像（装置 透過型電子顕微鏡（ＴＥＭ） 日立製 Ｈ−７６５０、加速電圧 １００ｋＶ、観察倍率５０万倍、傾斜角度 −６０°〜＋６０°、傾斜ステップ １°）を撮影した。次に、Ｆｉｎｄｕｃｉａｌ Ｍａｒｋｅｒ法により画像位置補正を行い、断面薄膜試料の３次元再構成像（再構成用ソフト ＩＭＯＤ３．９．３、表示用ソフト Ｍｅｒｃｕｒｙ Ｃｏｍｐｕｔｅｒ Ｓｙｓｔｅｍｓ，Ａｍｉｒａ）を得た。得られた３次元再構成像より、２５０ｎｍ×５０ｎｍの範囲を抽出し、アンカーコート層／無機酸化物層の界面における粗さ曲線より、その平均線から±１．５ｎｍを超える凹凸の数を求め、全体の凹凸の数に占める比率を下式１により算出する。

<Roughness ratio of interface and standard deviation of unevenness>
For the transparent barrier film, a cross-sectional thin film sample (with gold particles attached as a marker for reconstruction) was prepared by FIB-microsampling method (device Hitachi FB-2100, acceleration voltage 40 kV). Subsequently, a continuous tilt TEM image (apparatus transmission electron microscope (TEM) Hitachi H-7650, acceleration voltage 100 kV, observation magnification 500,000 times, tilt angle −60 ° to + 60 °, tilt step 1 °) was taken. Next, the image position was corrected by the Final Marker method to obtain a three-dimensional reconstructed image of the cross-sectional thin film sample (reconstruction software IMOD 3.9.3, display software Mercury Computer Systems, Amira). From the obtained three-dimensional reconstruction image, a range of 250 nm × 50 nm is extracted, and the number of irregularities exceeding ± 1.5 nm from the average line is obtained from the roughness curve at the anchor coat layer / inorganic oxide layer interface. The ratio of the total number of irregularities is calculated by the following formula 1.

Formula 1 = (number of irregularities exceeding ± 1.5 nm) / (total number of irregularities) × 100
Further, regarding the roughness curve of the anchor coat layer / inorganic oxide layer interface extracted as described above, the standard deviation was calculated using the heights of all the irregularities when an average line was drawn.

<Measurement of oxygen permeability>
The oxygen permeability was measured in accordance with the B method (isobaric method) defined in Japanese Industrial Standards JIS K7126-1987 “Plastic Film and Sheet Gas Permeability Test Method”. 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%.

<Measurement of water vapor transmission rate>
The water vapor transmission rate was measured in accordance with Method B (infrared sensor method) defined in Japanese Industrial Standards JIS K7129-2008 “Plastics—Films and Sheets—Method for Determining Water Vapor Transmission Rate (Equipment Measurement Method)”. This measurement was performed using Permtran 3/33 manufactured by Modern Control in an environment where the temperature was 40 ° C. and the relative humidity was 90%.

<Adjustment of anchor coating solution A for anchor coating layer>
In a diluting solvent, 2.5 times (weight ratio) of acrylic polyol is mixed with 2- (epoxycyclohexane) ethyltrimethylsilane (hereinafter referred to as EETMS), and further a tin chloride / methanol solution (0.003 mol / wt). g) was added so that it would be 1/135 mol with respect to EETMS, and then tolylene diisocyanate was mixed so that the NCO group was equivalent to the OH group of the acrylic polyol to prepare anchor coat liquid A. did. Hereinafter, the solution thus obtained is referred to as “anchor coating solution A”.

<Adjustment of anchor coating liquid B for anchor coating layer>
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 “anchor coating solution B”.

<Adjustment of anchor coating solution C for anchor coating layer>
Tolylene diisocyanate and diphenylmethane diisocyanate are added as a curing agent to a dispersion containing a polyester resin having a number average molecular weight of about 40,000 and an acid value of 20 mg KOH / g, so that the solid content concentration becomes 5%. The mixture was diluted with a methyl ethyl ketone / toluene mixed solvent and stirred for 10 minutes. Hereinafter, the solution thus obtained is referred to as “anchor coating liquid C”.

<Adjustment of anchor coating liquid D for anchor coating layer>
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 2% by mass, followed by stirring for 10 minutes. That is, the anchor coating liquid B was diluted with ethyl acetate so that the solid content concentration was 2% by mass without mixing a mixture containing xylylene diisocyanate and isophorone diisocyanate at a mass ratio of 60:40. Hereinafter, the solution thus obtained is referred to as “anchor coating solution D”.

<Preparation of barrier coating liquid E for gas barrier coating layer>
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. Next, 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.

  Next, the hydrolysis solution and the PVA solution were mixed and stirred for 30 minutes to prepare a solution. Hereinafter, the solution thus obtained is referred to as “barrier coating liquid E”.

<Preparation of barrier coating solution F for gas barrier coating layer>
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”. In addition, PVA
PVA solution was prepared by mixing water, isopropyl alcohol and water. 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”. Furthermore, 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, the solution thus obtained is referred to as “barrier coating liquid F”.

<Example 1>
In the production of a PET film, the film was stretched longitudinally by 3.0 times through heating rollers having different peripheral speeds. Next, a coating liquid mainly composed of polyester urethane prepared from aromatic carboxylic acid, aliphatic carboxylic acid, polyol and isocyanate by Meyer bar coating method was applied on one main surface of the PET film. This coating film was dried in the preheating part, and then stretched by 3.1 times in the transverse direction. Furthermore, the heat setting process was performed at the temperature of 220 degreeC. Next, corona discharge treatment was performed on the surface of the easily adhesive coat layer. In this way, the PET film used as the base film has a thickness of 12 μm, and the easy-adhesion PET on which the easy-adhesion coat layer having a thickness of 0.03 μm and subjected to corona discharge treatment is formed. A film was prepared.

  Then, the anchor coating liquid A was apply | coated by the gravure coating method on the easily bonding coat layer of an easily bonding PET film, and the anchor coating layer with a thickness of 0.04 micrometer was obtained by drying this coating film. Subsequently, an inorganic oxide layer made of silicon oxide and having a thickness of 25 nm was formed on the anchor coat layer by a vacuum vapor deposition apparatus using an induction heating method. Next, the barrier coating liquid E was applied onto the inorganic oxide layer by a gravure coating method, and this coating film was dried by heating to obtain a gas barrier coating layer having a thickness of 0.5 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 GF1”.

Next, the transparent gas barrier film GF1 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 layer. As the heat-sealable resin layer, a 60 μm-thick linear low-density polyethylene film (manufactured by Tosero Co., Ltd., TUX-TCS) 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 onto the gas barrier coating layer by a gravure coating method so that the coating amount after drying was 4.0 g / m ^2, and then this laminate was cured in a thermostatic chamber at 50 ° C. for 5 days. . The transparent packaging material was completed as mentioned above. Hereinafter, this transparent packaging material is referred to as “transparent packaging material HZ1”.

<Example 2>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1, except that the anchor coating liquid B is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF2”, and the transparent packaging material is referred to as “transparent packaging material HZ2”.

<Example 3>
The transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1 were described except that the anchor coating liquid C was used instead of the anchor coating liquid A and the thickness of the anchor coating layer was 0.10 μm. A transparent gas barrier film and a transparent packaging material were produced by the same method. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF3”, and the transparent packaging material is referred to as “transparent packaging material HZ3”.

<Example 4>
The transparent gas barrier film GF3 and the transparent packaging material HZ3 in Example 3 are the same as described above except that the barrier coating F is used instead of the barrier coating liquid E and the thickness of the gas barrier coating layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF4”, and the transparent packaging material is referred to as “transparent packaging material HZ4”.

<Example 5>
The transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1 were explained except that instead of the easy-adhesion PET film, a PET film having a thickness of 12 μm without an easy-adhesion coat layer was used as the base film. A transparent gas barrier film and a transparent packaging material were produced by the same method. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF5”, and the transparent packaging material is referred to as “transparent packaging material HZ5”.

<Example 6>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF5 and the transparent packaging material HZ5 in Example 5 except that the anchor coating liquid B is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF6”, and the transparent packaging material is referred to as “transparent packaging material HZ6”.

<Example 7>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF6 and the transparent packaging material HZ6 in Example 6 except that the barrier coating liquid F is used instead of the barrier coating liquid E. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF7”, and the transparent packaging material is referred to as “transparent packaging material HZ7”.

<Example 8>
The transparent gas barrier film GF7 and the transparent packaging material HZ7 in Example 7 are the same as described in Example 7, except that the anchor coating liquid C is used instead of the anchor coating liquid A and the thickness of the anchor coating layer is 0.10 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF8”, and the transparent packaging material is referred to as “transparent packaging material HZ8”.

<Example 9>
Instead of forming an inorganic oxide layer made of silicon oxide having a thickness of 25 nm by a vacuum vapor deposition apparatus using an induction heating method, an inorganic film having a thickness of 15 nm made of aluminum oxide is formed by a vacuum vapor deposition apparatus using an electron beam heating method. A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1 except that the oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF9”, and the transparent packaging material is referred to as “transparent packaging material HZ9”.

<Example 10>
Except that the anchor coating liquid B is used instead of the anchor coating liquid A and the thickness of the anchor coating layer is 0.50 μm, the same as described for the transparent gas barrier film GF9 and the transparent packaging material HZ9 in Example 9. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF10”, and the transparent packaging material is referred to as “transparent packaging material HZ10”.

<Example 11>
The transparent gas barrier film GF10 and the transparent packaging material HZ10 in Example 10 are the same as described above except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF11”, and the transparent packaging material is referred to as “transparent packaging material HZ11”.

<Example 12>
The transparent gas barrier film GF10 and the transparent packaging material HZ10 in Example 10 were explained except that a PET film having a thickness of 12 μm without an easy adhesion coating layer was used instead of the easy adhesion PET film as the base film. A transparent gas barrier film and a transparent packaging material were produced by the same method. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF12”, and the transparent packaging material is referred to as “transparent packaging material HZ12”.

<Example 13>
The transparent gas barrier film GF12 and the transparent packaging material HZ12 in Example 12 are the same as those described in Example 12, except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF13”, and the transparent packaging material is referred to as “transparent packaging material HZ13”.

<Example 14>
Instead of using an easy-adhesion PET film as the base film, a PET film having a thickness of 12 μm without an easy-adhesion coat layer and a reactive ion etching treatment on one surface of the PET film was used. Produced a transparent gas barrier film and a transparent packaging material by the same method as described for the transparent gas barrier film GF10 and the transparent packaging material HZ10 in Example 10. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF14”, and the transparent packaging material is referred to as “transparent packaging material HZ14”.

<Example 15>
The transparent gas barrier film GF14 and the transparent packaging material HZ14 in Example 14 are the same as described in Example 14 except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF15”, and the transparent packaging material is referred to as “transparent packaging material HZ15”.

<Example 16>
Instead of forming an inorganic oxide layer made of silicon oxide having a thickness of 25 nm by a vacuum vapor deposition apparatus using an induction heating method, an inorganic film having a thickness of 10 nm made of magnesium oxide by a vacuum vapor deposition apparatus using an electron beam heating method. A transparent gas barrier was formed in the same manner as described for the transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1, except that an oxide layer was formed and the anchor coating liquid B was used instead of the anchor coating liquid A. A film was produced. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF16”, and the transparent packaging material is referred to as “transparent packaging material HZ16”.

<Example 17>
Instead of forming an inorganic oxide layer made of magnesium oxide with a thickness of 10 nm by a vacuum vapor deposition apparatus using an electron beam heating method, a thickness of 30 nm made of tin oxide with a vacuum vapor deposition apparatus using an electron beam heating method A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film GF16 and the transparent packaging material HZ16 in Example 16 except that the inorganic oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF17”, and the transparent packaging material is referred to as “transparent packaging material HZ17”.

<Comparative Example 1>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1, except that the anchor coating liquid D is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF101”, and the transparent packaging material is referred to as “transparent packaging material HZ101”.

<Comparative example 2>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF5 and the transparent packaging material HZ5 in Example 5 except that the anchor coating liquid D is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF102”, and the transparent packaging material is referred to as “transparent packaging material HZ102”.

<Comparative Example 3>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF9 and the transparent packaging material HZ9 in Example 9 except that the anchor coating liquid D is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF103”, and the transparent packaging material is referred to as “transparent packaging material HZ103”.

<Comparative example 4>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF12 and the transparent packaging material HZ12 in Example 12 except that the anchor coating liquid D is used instead of the anchor coating liquid B. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF104”, and the transparent packaging material is referred to as “transparent packaging material HZ104”.

<Comparative Example 5>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF16 and the transparent packaging material HZ16 in Example 16 except that the anchor coating liquid D is used instead of the anchor coating liquid B. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF105”, and the transparent packaging material is referred to as “transparent packaging material HZ105”.

<Comparative Example 6>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF17 and the transparent packaging material HZ17 in Example 17 except that the anchor coating liquid D is used instead of the anchor coating liquid B. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF106”, and the transparent packaging material is referred to as “transparent packaging material HZ106”.

  As shown in Tables 1 and 2, since the transparent gas barrier films GF101 to GF106 have many large irregularities at the anchor coat layer / inorganic oxide layer interface, the values of oxygen permeability and water vapor permeability are high, and the gas barrier property Became low. Similarly, the transparent packaging materials HZ101 to HZ106 also had high values of oxygen permeability and water vapor permeability and low gas barrier properties.

  In contrast, the transparent gas barrier films GF1 to 17 and the transparent packaging materials HZ1 to HZ17 have lower values of oxygen permeability and water vapor permeability than the transparent gas barrier films GF101 to 106 and the transparent packaging materials HZ101 to HZ106. High gas barrier performance was demonstrated.

<Example 18>
A transparent gas barrier film and a transparent packaging material were produced in the same manner as described for the transparent gas barrier film GF18 and the transparent packaging material HZ18 in Example 1 except that the barrier coating liquid E was not applied. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF18”, and the transparent packaging material is referred to as “transparent packaging material HZ18”.

<Comparative Example 7>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF18 and the transparent packaging material HZ18 in Example 18 except that the anchor coating liquid D is used instead of the anchor coating liquid A. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF107”, and the transparent packaging material is referred to as “transparent packaging material HZ107”.
As shown in Tables 3 to 4, since the transparent gas barrier film GF107 has many large irregularities at the anchor coat layer / inorganic oxide layer interface, the values of oxygen permeability and water vapor permeability are high, and the gas barrier property is low. It became a thing. Similarly, the transparent packaging material HZ107 also had high values of oxygen permeability and water vapor permeability and low gas barrier properties.

  On the other hand, the transparent gas barrier film GF18 and the transparent packaging material HZ18 showed lower gas permeability and water vapor permeability and higher gas barrier performance than the transparent gas barrier film GF107 and the transparent packaging material HZ107.

<Example 19>
Transparent gas barrier film GF1 in Example 1, transparent packaging, except that a nylon film with a thickness of 15 μm is used instead of the easy-adhesion PET film as the base film and the anchor coating liquid B is used instead of the anchor coating liquid A A transparent gas barrier film and a transparent packaging material were produced by the same method as described for the material HZ1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF19”, and the transparent packaging material is referred to as “transparent packaging material HZ19”.

<Example 20>
Instead of forming an inorganic oxide layer made of silicon oxide having a thickness of 25 nm by a vacuum vapor deposition apparatus using an induction heating method, an inorganic film having a thickness of 15 nm made of aluminum oxide is formed by a vacuum vapor deposition apparatus using an electron beam heating method. A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film GF19 and the transparent packaging material HZ19 in Example 19 except that the oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF20”, and the transparent packaging material is referred to as “transparent packaging material HZ20”.

<Example 21>
The transparent gas barrier film GF20 and the transparent packaging material HZ20 in Example 20 are the same as described in Example 20, except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF21”, and the transparent packaging material is referred to as “transparent packaging material HZ21”.

<Example 22>
In the production of a nylon film, a water dispersible polyester polyurethane polyurea resin was applied to one main surface of the nylon film by a Meyer bar coating method. Next, it 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. In this way, the thickness of the base film was set to 15 μm, and an easy adhesion coating layer having a thickness of 0.05 μm was formed thereon. Next, corona discharge treatment was performed on the surface of the easily adhesive coat layer. In this way, an easy-adhesive nylon film having a nylon film thickness of 15 μm as a base film and an easy-adhesion coat layer having a thickness of 0.05 μm and a corona discharge treatment formed on the surface is formed. Produced. A transparent gas barrier film and a transparent packaging material were produced in the same manner as described for the transparent gas barrier film GF19 and the transparent packaging material HZ19 in Example 19 except that this easily adhesive nylon film was used instead of the nylon film. . Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF22”, and the transparent packaging material is referred to as “transparent packaging material HZ22”.

<Example 23>
The transparent gas barrier film GF22 and the transparent packaging material HZ22 in Example 22 are the same as described in Example 22 except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF23”, and the transparent packaging material is referred to as “transparent packaging material HZ23”.

<Example 24>
Instead of forming an inorganic oxide layer made of silicon oxide having a thickness of 25 nm by a vacuum vapor deposition apparatus using an induction heating method, an inorganic film having a thickness of 15 nm made of aluminum oxide is formed by a vacuum vapor deposition apparatus using an electron beam heating method. A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film GF22 and the transparent packaging material HZ22 in Example 22 except that the oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF24”, and the transparent packaging material is referred to as “transparent packaging material HZ24”.

<Example 25>
The transparent gas barrier film GF24 and the transparent packaging material HZ24 in Example 24 are the same as described in Example 24 except that the barrier coating liquid F is used instead of the barrier coating liquid E and the thickness of the anchor coat layer is 0.30 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF25”, and the transparent packaging material is referred to as “transparent packaging material HZ25”.

<Example 26>
The transparent gas barrier film GF24 and the transparent packaging material HZ24 in Example 24 are the same as described in Example 24 except that the anchor coating liquid C is used instead of the anchor coating liquid B and the thickness of the anchor coat layer is 0.10 μm. A transparent gas barrier film and a transparent packaging material were produced by the method described above. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF26”, and the transparent packaging material is referred to as “transparent packaging material HZ26”.

<Comparative Example 8>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF19 and the transparent packaging material HZ19 in Example 19 except that the anchor coating liquid D is used instead of the anchor coating liquid B. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF108”, and the transparent packaging material is referred to as “transparent packaging material HZ108”.

  As shown in Tables 5 to 6, the transparent gas barrier film GF108 has large irregularities at the anchor coat layer / inorganic oxide layer interface, so the values of oxygen permeability and water vapor permeability are high, and the gas barrier property is low. It became a thing. Similarly, the transparent packaging material HZ108 also had high oxygen permeability and water vapor permeability and low gas barrier properties.

  On the other hand, the transparent gas barrier films GF19 to GF26 and the transparent packaging materials HZ19 to GF26 have lower values of oxygen permeability and water vapor permeability than the transparent gas barrier film GF108 and the transparent packaging material HZ108, and exhibit high gas barrier performance. It was.

<Example 27>
Other than using an OPP film with a thickness of 20 μm instead of the easy-adhesion PET film as the base film, and using the anchor coating liquid B instead of the anchor coating liquid A, and setting the thickness of the anchor coat layer to 1.00 μm Produced a transparent gas barrier film and a transparent packaging material in the same manner as described for the transparent gas barrier film GF1 and the transparent packaging material HZ1 in Example 1. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF27”, and the transparent packaging material is referred to as “transparent packaging material HZ27”.

<Example 28>
Instead of forming an inorganic oxide layer made of silicon oxide having a thickness of 25 nm by a vacuum vapor deposition apparatus using an induction heating method, an inorganic film having a thickness of 15 nm made of aluminum oxide is formed by a vacuum vapor deposition apparatus using an electron beam heating method. A transparent gas barrier film was produced in the same manner as described for the transparent gas barrier film GF27 and the transparent packaging material HZ27 in Example 27 except that the oxide layer was formed. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF28”, and the transparent packaging material is referred to as “transparent packaging material HZ28”.

<Example 29>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF28 and the transparent packaging material HZ28 in Example 28 except that the barrier coating liquid F is used instead of the barrier coating liquid E. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF29”, and the transparent packaging material is referred to as “transparent packaging material HZ29”.

<Comparative Example 9>
A transparent gas barrier film and a transparent packaging material are produced in the same manner as described for the transparent gas barrier film GF27 and the transparent packaging material HZ27 in Example 27 except that the anchor coating liquid D is used instead of the anchor coating liquid B. did. Hereinafter, this transparent gas barrier film is referred to as “transparent gas barrier film GF109”, and the transparent packaging material is referred to as “transparent packaging material HZ109”. As shown in Tables 7 to 8, the transparent gas barrier film GF109 is composed of an anchor coat layer / inorganic oxidation Since there were many large unevenness | corrugations in the interface of a physical layer, the numerical value of oxygen permeability and water vapor permeability was high, and it became a thing with low gas barrier property. Similarly, for the transparent packaging material HZ109, the numerical values of oxygen permeability and water vapor permeability were high, and the gas barrier properties were low.

  On the other hand, the transparent gas barrier films GF27 to 29 and the transparent packaging materials HZ27 to HZ29 have low values of oxygen permeability and water vapor permeability and high gas barrier performance compared to the transparent gas barrier film GF109 and the transparent packaging material HZ109. It was.

Sectional drawing which shows schematically one form of the transparent packaging material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base film 2 ... Anchor coat layer 3 ... Inorganic oxide layer 4 ... Gas barrier coating layer 5 ... Adhesive layer 6 ... Heat-sealable resin layer 10 ... Transparent gas barrier film 20 ... Transparent packaging material

Claims (8)

  A transparent gas barrier film in which an anchor coat layer is formed on at least one surface of a base film, and an inorganic oxide layer formed by a vapor deposition method is further formed on the anchor coat layer, and the anchor coat layer and When a three-dimensional reconstructed image is obtained by taking a continuous tilt TEM image (−60 ° to + 60 °, 1 ° step) at the interface with the inorganic oxide layer and then performing image position correction by the Fiducial Marker method. As for the roughness curve at the interface, the number of irregularities exceeding ± 1.5 nm from the average line accounts for 12% or less of the total number of irregularities, and the roughness curve at the interface is all from the average line. The standard deviation of the heights of the irregularities is less than 1.0, and the standard deviation of the heights of all the irregularities from the average line in the interface roughness curve is less than 1.0. A transparent gas barrier film characterized by that.   2. The transparent gas barrier according to claim 1, wherein the inorganic oxide layer is made of a material selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide, tin oxide, and a mixture containing two or more thereof. the film.   The transparent gas barrier film according to claim 1, wherein the base film is a plastic film.   The transparent gas barrier film according to any one of claims 1 to 3, further comprising a gas barrier coating layer formed on the inorganic oxide layer and made of a mixture containing a transparent resin and an inorganic substance. .   The gas barrier coating layer 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 transparent gas barrier film according to claim 4, wherein the transparent gas barrier film is formed by drying the coated film.   6. The transparent gas barrier film according to claim 5, 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 layer 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 and the inorganic oxide layer. The transparent gas barrier film according to claim 6, wherein the transparent gas barrier film is formed by coating on and drying the coating film thus obtained.   A laminate of the transparent gas barrier film according to any one of claims 1 to 7 and a heat-sealable resin layer that is bonded to the transparent gas barrier film and faces the base film with the inorganic oxide layer interposed therebetween. A transparent packaging material characterized by the above.

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