JP2007223286A - High-adhesion transparent gas-barrier film and high-adhesion transparent gas-barrier laminate using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent gas-barrier film having an excellent transparency and gas-barrier performance and especially excellent adhesion on being wetted and a transparent gas-barrier laminate using it. <P>SOLUTION: A polyamide resin film is overlaid successively with the first anchor coat layer composed of an anchor coat liquid based on one or more of bifunctional isocyanate monomers and isocyanate compounds comprising derivatives of adduct, buret, and isocyanurate type trifunctional monomers and the second anchor coat layer composed of an anchor coat liquid comprising a trifunctional organosilane of formula R<SB>1</SB>Si(OR<SB>2</SB>) (wherein R<SB>1</SB>is one of amino, isocyanate, sulfoxide and epoxy groups, and R<SB>2</SB>is an alkyl group), a polyol compound and an isocyanate compound, and further the second anchor coat layer is overlaid with a transparent vapor-deposited thin-film layer composed of an organic oxide and a gas-barrier coating layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transparent gas barrier film that is particularly excellent in transparency and gas barrier properties required for packaging films used for packaging foods, medical drugs, precision electronic parts, and the like, and also has excellent adhesion when wet. The present invention relates to a transparent gas barrier laminate.

  In recent years, packaging materials used for the packaging of foods, pharmaceuticals, precision electronic components, etc. have been used to maintain the taste and freshness by suppressing the alteration of contents, especially the oxidation and alteration of proteins and oils and fats in food applications. In pharmaceutical applications, in order to suppress the alteration and scattering of medicinal components and maintain their efficacy, and in precision electronic parts applications, in order to prevent corrosion and insulation failure of metal parts, oxygen, water vapor, In addition, it is necessary to prevent the influence of the gas that alters the contents, and it is required to have a gas barrier property that blocks these gases.

  Among these packaging materials, there are various uses for packaging materials in which polyamide-based resin films with excellent impact resistance, puncture resistance, bending resistance, wear resistance, etc. are used as base films from the viewpoint of content protection. Widely used. Such a packaging material is also required to have a high gas barrier property for preventing the deterioration of the quality of the contents as described above.

  In order to satisfy such demands, a polyamide resin film as a base film laminated with a metal foil such as an aluminum foil as a gas barrier layer, polyvinylidene chloride (PVDC), ethylene vinyl alcohol copolymer (EVOH) ), Metaxylenediamine-6 nylon (MXD6-nylon) or the like laminated by a method such as coating or coextrusion has been developed and used in various ways.

  However, a packaging material provided with a metal foil such as an aluminum foil is excellent in gas barrier properties, but the contents cannot be confirmed through it, and must be treated as non-combustible material at the time of disposal after use. In the inspection after filling the contents, the metal detector cannot be used, and since it does not transmit microwaves, it is not suitable as a packaging material for microwave ovens. there were. Moreover, although what laminated | stacked PVDC is cheap and has moderate gas barrier property, there existed a problem that a toxic gas generate | occur | produces at the time of incineration. Furthermore, the gas barrier property of the gas barrier laminate film in which the thin films of EVOH and MXD-6 nylon are laminated has a high environmental dependency, and there is a problem that the initial barrier property is greatly deteriorated in a high temperature / high humidity environment. .

  Therefore, in order to overcome these disadvantages, for example, a vapor deposition thin film layer made of an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, or the like, as described in Patent Document 1 or Patent Document 2, is used. A vapor deposition film formed on a polymer film by vapor deposition thin film forming means such as sputtering or the like has been developed. These vapor-deposited films have transparency and gas barrier properties against oxygen, water vapor, and the like, and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with a metal foil or the like.

However, a transparent gas barrier film in which a transparent vapor-deposited thin film layer of an inorganic oxide is simply provided on a polyamide-based resin film ensures high adhesion at the interface between the polyamide-based resin film and the transparent vapor-deposited thin film layer, especially when wet. Can not. For example, after making a packaging bag using a transparent gas barrier laminate obtained by laminating a heat-sealable resin layer on a transparent vapor-deposited thin film layer of such a transparent gas barrier film, the liquid content is filled there. When stored as such, the adhesive force between the polyamide resin film and the inorganic oxide vapor-deposited thin film layer in the transparent gas barrier laminate is lowered, and in the worst case, delamination may occur. In addition, packaging materials that use polyamide-based resin film as a base film have many packaging applications for heavy objects such as liquids that require high strength due to their high toughness. In such a case, the decrease in the adhesive strength when wet as described above is often a problem.

  In order to solve such problems, the surface of the polyamide-based resin film is subjected to an easy adhesion treatment by in-line pretreatment in a vapor deposition apparatus using a plasma treatment, and is made of an inorganic oxide laminated thereon. Various attempts have been made to improve the adhesion to the deposited thin film layer (see, for example, Patent Documents 3 and 4).

  However, since the polyamide-based resin film has a high affinity with water due to its structural characteristics, the laminate is formed by forming the transparent vapor-deposited thin film layer made of an inorganic oxide after directly performing the plasma treatment on the surface. In the case of making, the adhesiveness can be obtained when dried, but when wet or when it is stored for a long time after being filled with moisture-containing contents, moisture penetrates into the treated surface by the above plasma treatment, and the adhesion force There was a fear that would deteriorate significantly.

Moreover, in order to improve the weak adhesion between the polyamide resin film and the transparent vapor-deposited thin film layer made of an inorganic oxide, an anchor coat layer mainly composed of a urethane compound was provided on one side of the polyamide resin film. Thereafter, various transparent gas barrier films in which a transparent vapor-deposited thin film layer made of an inorganic oxide is laminated have been proposed (see, for example, Patent Documents 5 and 6).
U.S. Pat. No. 3,442,686 Japanese Utility Model Publication 52-24608 JP-A-6-65712 Japanese Patent Laid-Open No. 2001-138430 JP 2001-81217 A However, the anchor coat layer made of an anchor coat liquid mainly composed of a urethane compound shows high adhesion to the polyamide resin film, but is between the transparent vapor-deposited thin film layer made of an inorganic oxide. However, it still has a problem that the adhesion is greatly reduced when it is wet or when it is stored for a long time after being filled with water-containing contents.

  The present invention has been made to solve the above-mentioned problems, and is a polyamide-based resin film constituting a strong adhesion transparent gas barrier film, and a transparent vapor-deposited thin film layer made of an inorganic oxide provided on top of the polyamide-based resin film. When the adhesion strength between the two, particularly when wet, is greatly improved, and a heat-sealable resin layer is laminated on the transparent gas barrier film to form a transparent gas barrier laminate, which is used as a packaging film In addition, a strong adhesion transparent gas barrier film and a transparent gas barrier laminate using the same that are less likely to cause problems such as broken bags and delamination even when applied to packaging for contents such as moisture-containing foods. For the purpose of provision.

In order to solve the above problems, the invention according to claim 1 is characterized in that at least one surface of a polyamide-based resin film is trifunctionalized with a bifunctional isocyanate monomer or adduct, burette, or isocyanurate type. A first anchor coat layer comprising an anchor coat liquid mainly composed of an isocyanate compound which is a derivative of a monomer, and a general formula R ₁ Si (OR ₂ ) (R ₁ = amino group, isocyanate group, sulfoxide group, epoxy group, etc .; R ₂ = alkyl group) and a second anchor of a base film in which a second anchor coat layer made of an anchor coat liquid, which is a composite of a trifunctional organosilane represented by R ₂ = alkyl group, and a polyol compound and an isocyanate compound, is sequentially laminated. A transparent vapor-deposited thin film layer made of an inorganic oxide and a gas barrier coating layer are formed on the coat layer. A strong adhesion transparent gas barrier film characterized in that it is next stacked.

  In addition, the invention according to claim 2 is characterized in that the strong adhesion transparent gas barrier film according to claim 1 is characterized in that the inorganic oxide is any one of aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. To do.

  Furthermore, the invention according to claim 3 is the strong adhesion transparent gas barrier film according to claim 1 or 2, wherein the gas barrier coating layer comprises a water-soluble polymer, (a) one or more metal alkoxides and It is characterized by comprising a gas barrier coating liquid mainly composed of a hydrolyzate or an aqueous solution containing at least one of (b) tin chloride or a water / alcohol mixed solution.

  Furthermore, the invention according to claim 4 is the strong adhesion transparent gas barrier film according to any one of claims 1 to 3, wherein the thickness of the first anchor coat layer and the second anchor coat layer is 0.005 to 0.005. It is characterized by being in the range of 1 μm.

  Furthermore, the invention according to claim 5 is the strong adhesion transparent gas barrier film according to any one of claims 1 to 4, wherein the first anchor coat layer and the second anchor coat layer are anchor coats constituting each of them. It is characterized by being subjected to curing treatment at a temperature of 30 to 80 ° C. after the thin films made of the liquid are sequentially laminated.

  Furthermore, in the invention described in claim 6, a heat-sealable resin layer is provided on the gas barrier coating layer of the strong adhesion transparent gas barrier film according to any one of claims 1 to 5 via an adhesive layer. It is a strong adhesion transparent gas-barrier laminated body characterized by being made.

  Furthermore, the invention according to claim 7 is the normal laminate at the boundary surface between the gas barrier coating layer and the heat sealable resin layer of the strong adhesion transparent gas barrier film in the strong adhesion transparent gas barrier laminate according to claim 6. The strength is 5.0 N / 15 mm or more, and the wet laminate strength when water is immersed in the boundary surface is 2.5 N / 15 mm or more.

  Since the strong adhesion transparent gas barrier film of the present invention and the strong adhesion transparent gas barrier laminate using the same have the above-described configuration, the first anchor coat is of course excellent in transparency and gas barrier properties. The layer is firmly adhered to the polyamide-based resin film, and the second anchor coat layer is firmly adhered to the transparent vapor-deposited thin film layer made of an inorganic oxide. Adhesion when wet is improved. For example, when it is applied as a packaging material for liquid contents and moisture-containing contents that require excellent water-resistant adhesion, bag breakage and delamination problems occur. No longer.

Further, in the strong adhesion transparent gas barrier film of the present invention, the first anchor coat layer and the second anchor coat layer constituting a part thereof are laminated on the polyamide resin film in-line in the same processing machine. Therefore, the process can be simplified and can be supplied at low cost.

  Furthermore, the strong adhesion transparent gas barrier film of the present invention and the strong adhesion transparent gas barrier laminate using the same are not limited to the liquid and moisture-containing contents described above, but also other foods, medical drugs, precision electronic components, etc. It can be suitably used as a packaging application, and has a wide application range.

  Hereinafter, the embodiment of the present invention will be described in more detail.

  FIG. 1 is an explanatory view showing a schematic cross-sectional structure of a strongly adherent transparent gas barrier film of the present invention. Moreover, FIG. 2 is explanatory drawing which shows the general | schematic cross-section structure of the strong_contact | adherence transparent gas-barrier laminated body of this invention.

  In the strong adhesion transparent gas barrier film 20, the first anchor coat layer 2 and the second anchor coat layer 3 are sequentially laminated on one surface of the polyamide-based resin film 1, and further on the second anchor coat layer 3, A transparent vapor-deposited thin film layer 4 made of an inorganic oxide and a gas barrier coating layer 5 are sequentially laminated. Further, in the strong adhesion transparent gas barrier laminate 30 of the present invention, the heat-sealable resin layer 7 is sequentially formed on the gas barrier coating layer 5 of the strong adhesion transparent gas barrier film 20 having the above-described configuration via the adhesive layer 6. It is a laminated structure.

  The polyamide-based resin film 1 serving as a base film is preferably a transparent film substrate if possible in order to make use of the transparency of the transparent vapor-deposited thin film layer 4 described later. The constituent material is not particularly limited as long as it can support the transparent vapor-deposited thin film layer 4 made of an inorganic oxide, and specific examples include homopolyamide, copolyamide, or a mixture thereof.

  Examples of the homopolyamide include polycaprolactam (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), poly-ω-undecanoic acid (nylon 11), poly Laurin lactam (nylon 12), polyethylenediamine adipamide (nylon 2,6), polytetramethylene adipamide (nylon 4,6), polyhexamethylene didipamide (nylon 6,6), polyhexamiethylene Bacamide (nylon 6,10), polyhexamethylene adipamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), polydeca Methylene sebacamide (nylon 10,10), polydecamethylene dodecamide (nylon 12,12) Metaxylenediamine -6 nylon (MXD6) and the like.

Examples of the above copolyamide include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamytylene diammonium sebacate copolymer, hexamethylene diammonium adipate / hexame. Examples thereof include a tylene diammonium sebacate copolymer and a caprolactam / hexamethylene diammonium adipate / hexamytylene diammonium sebacate copolymer.
Among these, an appropriate one may be selected and used in consideration of the use environment as the transparent gas barrier film or the transparent gas barrier laminate, the type of package, the workability and the economy.

Furthermore, for the purpose of imparting flexibility to the polyamide-based resin film 1 made of these materials and improving bending pinhole resistance, plasticizers of aromatic sulfonamides, p-hydroxybenzoic acid, and esters are added. It is also possible to blend, or to blend a low elastic modulus elastomer component or lactam. Examples of the elastomer component include ionomer resin, modified polyolefin resin, thermoplastic polyurethane, polyether block amide, polyester block amide, polyether ester amide elastomer, modified acrylic rubber, polyester elastomer, ethylene-acrylate copolymer modified ethylene. Examples include propylene rubber.

  On the other hand, the first anchor coat layer 2 provided on such a polyamide-based resin film 1 is an isocyanate which is a bifunctional isocyanate monomer or a derivative of a trifunctional monomer of adduct, burette or isocyanurate type. It consists of an anchor coat liquid mainly composed of a compound.

  Examples of the isocyanate compound include various diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and hydrogenated products thereof. Based monomers. In addition, adduct types obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette types reacted with water, and trimers utilizing self-polymerization of isocyanate groups. A trifunctional derivative such as (isocyanurate) type or a polyfunctional derivative higher than that may be used.

  The first anchor coat layer 2 is prepared, for example, as a coating liquid (anchor coat liquid) containing the above-described isocyanate compound in a solid content ratio of 0.05 to 5 wt%, preferably 0.1 to 2 wt%. Coating on the polyamide resin film 1 by a known coating method such as gravure coating method, roll coating method, comma coating method, cast coating method, calendar coating method, bar coating method, die coating method, etc. Good. The first anchor coat layer 2 is preferably a thin layer. Specifically, the thickness of the first anchor coat layer 2 may be in the range of about 0.005 to 1 μm. When the thickness is less than 0.005 μm, it is difficult to ensure sufficient adhesion strength to the polyamide resin film 1. Further, even if the thickness exceeds 1 μm, it is not economical because an effect of further performance improvement cannot be expected.

  By providing the first anchor coat layer 2 having such a configuration on the polyamide-based resin film 1, it becomes possible to ensure strong water-resistant adhesion between them. However, if the first anchor coat layer 2 is provided and only the transparent vapor-deposited thin film layer made of an inorganic oxide is provided on the first anchor coat layer 2, the water-resistant adhesion is insufficient depending on the application used, or the adhesion strength is lowered due to aging. May be seen. Therefore, in the present invention, the second anchor coat layer 3 is further provided on the first anchor coat layer 2 to further improve and stabilize the water-resistant adhesion.

  This second anchor coat layer 3 is provided on the first anchor coat layer 2 to strengthen the adhesion force mainly with the vapor-deposited thin film layer 4 of the inorganic oxide, and to reduce the adhesion strength when wet. This contributes to the prevention of lamination and the prevention of deterioration of gas barrier properties.

The second anchor coat layer 3 is composed of a trifunctional organosilane and a polyol represented by the general formula R ₁ Si (OR ₂ ) (R ₁ = amino group, isocyanate group, sulfoxide group, epoxy group, etc., R ₂ = alkyl group). It is formed from a composite of a compound and an isocyanate compound.

Examples of the polyol compound include polyether polyol, polyester polyol, polyester urethane polyol, acrylic polyol, polycaprolactone polyol, and polycarbonate polyol. As the isocyanate compound, various diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate and hydrogenated products thereof. Monomers, adduct types obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette types reacted with water, and trimers utilizing self-polymerization of isocyanate groups ( Examples thereof include trifunctional derivatives such as isocyanurate) type and higher polyfunctional derivatives.

  These first anchor coat layer 2 and second anchor coat layer 3 are additives such as various surfactants, antistatic agents, inorganic lubricants, organic lubricants, ultraviolet absorbers and the like within a range not impairing the effects of the present invention. Can also be included.

  As with the first anchor coat layer 2, the second anchor coat layer 3 is a known coating such as a gravure coat method, a roll coat method, a comma coat method, a cast coat method, a calendar coat method, a bar coat method, or a die coat method. The coating may be provided by a method. However, since the first anchor coat layer 2 is applied on the polyamide resin film 1 and wound into a roll as it is, a blocking phenomenon is likely to occur due to change over time. It is necessary to apply the second anchor coat layer 3 promptly. Therefore, it is more preferable to apply the first anchor coat layer and the second anchor coat layer with the same processing machine (in-line coat) by a two-head coater provided with two coating heads.

The thickness of the second anchor coat layer 3 is preferably about 0.005 to 1 g / m ² when dried. When the coating amount is less than 0.005 g / m ² , it is difficult to obtain sufficient adhesion strength with the polyamide resin film. On the other hand, if it exceeds 1 g / m ² , further improvement in performance cannot be expected and it is not economical.

  Thus, the thickness of the base film 10 in which the first anchor coat layer 2 and the second anchor coat layer 3 are sequentially provided on the polyamide-based resin film 1 takes into consideration the suitability for vapor deposition processing and the mechanical characteristics as a packaging material. Therefore, about 10 to 100 μm is preferable. Moreover, after providing the 2nd anchor coat layer 3 on the upper part of the polyamide-type resin film 1, it is preferable to perform a curing process for the base film 10 at the temperature of 30-80 degreeC. By performing the curing treatment, it is possible to promote the bonding of the components constituting the first anchor coat layer 2 and the second anchor coat layer 3 and to obtain a stronger and stronger adhesion force at an early stage.

  On the other hand, the transparent vapor-deposited thin film layer 4 made of an inorganic oxide provided on the second anchor coat layer 3 is made of silicon oxide, aluminum oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency. Any layer having a gas barrier property against oxygen, water vapor and the like may be used. There are various methods for forming the transparent vapor-deposited thin film layer 4 made of the inorganic oxide on the second anchor coat layer 3 of the base film 10, but vacuum vapor deposition, sputtering, ion plating, plasma vapor phase, and the like. A vapor deposition thin film forming method such as a growth method (CVD) can be exemplified. Among these, from the viewpoint of productivity, the vacuum vapor deposition method is the best at present. As a heating means in vacuum vapor deposition, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method, but considering the wide selection of evaporation materials, the electron beam heating method may be used. More preferred. Further, in order to improve the denseness of the transparent vapor-deposited thin film layer 4, it is also possible to form a film using a plasma assist method or an ion beam assist method. Furthermore, in order to increase the transparency of the deposited thin film layer, it is possible to use reactive deposition in which various gases such as oxygen are blown.

  The optimum thickness of the transparent vapor-deposited thin film layer 4 made of an inorganic oxide is preferably in the range of 1 to 500 nm, although the optimum condition varies depending on the type and configuration of the inorganic oxide used. However, if the thickness is less than 1 nm, it is difficult to form a uniform thin film, and it is difficult to sufficiently perform the function as a gas barrier layer. On the other hand, a thickness exceeding 500 nm makes it difficult to maintain the flexibility of the deposited thin film layer, and is liable to cause cracks due to external factors such as bending and pulling after film formation, and is not preferable because it is not economical.

  The gas barrier coating layer 5 provided on the transparent vapor deposition thin film layer 4 made of such an inorganic oxide protects the transparent vapor deposition thin film layer 4 and has a high gas barrier due to a synergistic effect with the transparent vapor deposition thin film layer 4. An aqueous solution or water / alcohol containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride. It is formed by applying a coating agent containing a mixed solution as a main ingredient and heating and drying.

  More specifically, a treatment in which a water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a metal alkoxide is directly or hydrolyzed in advance is performed. A mixed solution is prepared to prepare a coating agent, which is formed on the transparent vapor-deposited thin film layer 4 made of an inorganic oxide, and then heated and dried. Each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer used in the coating agent include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used for the coating agent of the present invention, the gas barrier property is most excellent, which is preferable. PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only several percent of acetic acid groups remain can be used from so-called partially saponified PVA in which several tens percent of acetic acid groups remain, and the type is not particularly limited.

Furthermore, the metal alkoxide is a compound represented by the general formula, M (OR) _n (M: metal such as Si, Ti, Al, Zr, R: alkyl group such as CH ₃ , C ₂ H _5, etc.). Specifically, tetramethoxysilane [Si (OC H ₃ ) ₄ ], tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triethoxyaluminum [Al (OC ₂ H ₅ ) ₃ ], trinormal propoxyaluminum [Al _{(O-n-C 3 H} 7) 3 ], triisopropoxyaluminum _{[Al (O-i-C 3} H 7) 3 ], tri-n-isobutoxy aluminum _{[Al (O-n-C 4} H 9) 3 ], tri isobutoxy aluminum _{[Al (O-i-C 4} H 9) 3 ], tetramethoxy titanium [Ti (OC H _{3) 4],} and the like. Among these, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

  The coating agent made of such a material requires known additives such as an isocyanate compound, a silane coupling agent, or a dispersant, a stabilizer, a viscosity modifier, and a colorant as long as the gas barrier property is not impaired. It is also possible to add as appropriate.

  As a coating method for the coating agent, conventionally known methods such as a commonly used dipping coating method, roll coating method, bar coating method, die coating method, spray coating method, and gravure coating method can be used.

When the thickness after drying is less than 0.01 μm, it is difficult to obtain a uniform coating film, so that the gas barrier effect is difficult to be obtained, and when the thickness exceeds 50 μm, Cracks are likely to occur. Therefore, the thickness is preferably in the range of 0.01 to 50 μm.

  Next, the strong adhesion transparent gas barrier laminate of the present invention will be described. The strong adhesion transparent gas barrier laminate 30 of the present invention is, as described above, also shown in FIG. 2, with the adhesive layer 6 interposed between the gas barrier coating layer 5 of the strong adhesion transparent gas barrier film 20 having the above-described configuration. The heat-sealable resin layer 7 is laminated.

Here, the adhesive layer 6 is a layer made of a general-purpose laminating adhesive. For example, poly (ester) urethane, polyester, polyamide, epoxy, poly (meth) acrylic, polyethyleneimine, ethylene- (meth) acrylic acid, polyvinyl acetate, (modified) polyolefin, polybutadiene It can be provided by an adhesive such as a (no) solvent type, an aqueous type, a hot melt type, etc. whose main component is a system, wax system, casein system or the like. Examples of the method for laminating the adhesive layer 6 include 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, and a fountain coating method. A coating method can be used. The thickness is preferably in the range of about 0.1 to 8 g / m ² (dry state).

  On the other hand, the heat-sealable resin layer 7 described above is provided so as to serve as a seal layer when producing a packaging container such as a bag-shaped package, and its constituent material is melted by heat. Can be fused to each other, specifically, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, other polyethylene resins, polypropylene, ethylene-propylene copolymer resin, polyester Resin, polyamide resin, ethylene-vinyl acetate copolymer and saponified product thereof, polycarbonate resin, polyacrylonitrile resin, nitrocellulose, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid Examples include ester copolymers, their cross-linked metal products, and biodegradable resins such as polylactic acid resins. Rukoto can. Moreover, the thickness should just be determined according to the objective, and generally should just exist in the range of 10-200 micrometers.

  As a method for laminating the heat-sealable resin layer 7 on the strong adhesion transparent gas barrier film 20, for example, a dry laminating method, a non-solvent laminating method, an extrusion laminating method, and other known laminating methods can be used. Moreover, in the strong adhesion transparent gas barrier laminate 30 of the present invention, the gas barrier of the strong adhesion transparent gas barrier film 20 is used for the purpose of improving rigidity and durability required as a packaging material in consideration of the use as a packaging material. After interposing a printing layer or other base film on the adhesive coating layer 5, the heat-sealable resin layer 7 may be laminated and used as a desired packaging material.

In the following, an embodiment of the present invention will be described in more detail. However, the present invention is not limited to these.
<Example 1>
As the polyamide-based resin film, a biaxially stretched nylon 6 film having a thickness of 15 μm and subjected to corona discharge treatment on one side was used. And the coating liquid prepared so that isophorone diisocyanate monomer might be 2 wt% of solid content was apply | coated to the corona discharge treatment surface of this polyamide-type resin film by the gravure coating method, and it dried at 100 degreeC and thickness was 0.05 micrometer. A first anchor coat layer was formed. Subsequently, a second anchor coat liquid having the following formulation is applied onto the first anchor coat layer by a gravure coat method, dried at 100 ° C., and a second anchor coat layer having a dried thickness of 0.1 μm is formed. Formed. Thereafter, in order to promote adhesion between both anchor coat layers, curing was performed at 60 ° C. for 2 days to obtain a base film. Then, the transparent vapor deposition thin film layer which consists of aluminum oxide with a thickness of 15 nm was laminated | stacked on the 2nd anchor coat layer of this base film by the vacuum vapor deposition apparatus by an electron beam heating system. Further, a gas barrier coating liquid having the composition shown below is applied on the transparent vapor-deposited thin film layer by a gravure coating method, dried by heating at 150 ° C., and a gas barrier coating layer (thickness 0.5 μm) is laminated. The strong adhesion transparent gas barrier film according to Example 1 of the present invention was obtained.

Subsequently, using the transparent gas barrier film, a polyurethane laminate adhesive (A616 / A65 manufactured by Mitsui Takeda Chemical Co., Ltd.) was applied onto the gas barrier coating layer surface of the transparent gas barrier film by a dry laminating method. The adhesive layer is laminated by coating at m ² , and a heat-sealable resin film made of a linear low-density polyethylene film (TUX-FCS made by Tosero) having a thickness of 50 μm is further laminated thereon, followed by 4 ° C. Curing was carried out for a day, and the strong adhesion transparent gas barrier laminate of the present invention according to Example 1 was obtained.
<Preparation of second anchor coating solution>
6 g of acrylic polyol (solid content 50%) and 0.6 g of isocyanate propyltrimethoxysilane were mixed and stirred and adjusted to a solid content of 20% with a diluting solvent. To 7 g of this solution, 1.5 g of a 60/40 weight ratio mixture of xylylene diisocyanate and isophorone diisocyanate (solid content 50%) was added, and a dilution solvent was added to adjust the solid content to 2%. Stirring was performed for 30 minutes to obtain a second anchor coat solution.

<Preparation of gas barrier coating solution>
89.6 g of hydrochloric acid (0.1N) is added to 10.4 g of tetraethoxysilane, and a hydrolyzed solution having a solid content of 3 wt% (in terms of SiO 2) which is hydrolyzed by stirring for 30 minutes, and 3 wt% water / isopropyl of polyvinyl alcohol. An alcohol solution (water: isopropyl alcohol = 90: 10 weight ratio) was mixed to obtain a gas barrier coating solution.
<Example 2>
The strong adhesion transparent gas barrier film and the strong adhesion transparent gas barrier property according to Example 2 were the same as in Example 1 except that the first anchor coat layer was provided with an adduct type of tolylene diisocyanate having a thickness of 0.1 μm. A laminate was obtained.
<Example 3>
Example 1 except that the first anchor coat layer is provided with a hexamethylene diisocyanate burette type having a thickness of 1 μm, and the transparent vapor-deposited thin film layer made of magnesium oxide is provided at a thickness of 15 nm by an electron beam heating vacuum deposition method. In the same manner, a strongly adhered transparent gas barrier film and a strongly adhered transparent gas barrier laminate according to Example 3 were obtained.
<Example 4>
Example 1 except that the first anchor coat layer is provided with an adduct type of xylylene diisocyanate having a thickness of 0.5 μm, and the transparent vapor-deposited thin film layer made of silicon oxide is provided with a thickness of 30 nm by a vacuum evaporation method using a resistance heating method. In the same manner, a strongly adhered transparent gas barrier film and a strongly adhered transparent gas barrier laminate according to Example 4 were obtained.
<Example 5>
The strong adhesion transparent gas barrier film and the strong adhesion transparent gas barrier laminate according to Example 5 were obtained in the same manner as in Example 1 except that curing for promoting adhesion of the anchor coat layer was performed at 35 ° C. for 5 days. Obtained.
<Example 6>
The first anchor coat layer and the second anchor coat layer were formed in the same manner as in Example 1 except that each of the first anchor coat layer and the second anchor coat layer was applied and formed inline by a gravure coat method. A transparent gas barrier film and a strong adhesion transparent gas barrier laminate were obtained.
<Example 7>
A strong adhesion transparent gas barrier film and a strong adhesion transparent gas barrier laminate according to Example 7 for comparison were obtained by the same operation as in Example 1 except that the first anchor coat layer was not provided.
<Example 8>
A strong adhesion transparent gas barrier film and a strong adhesion transparent gas barrier laminate according to Example 7 for comparison were obtained by the same operation as in Example 1 except that the second anchor coat layer was not provided.

  Oxygen permeability of strong adhesion transparent gas barrier films of Examples 1 to 8 and normal lamination strength and wet lamination strength of strong adhesion transparent gas barrier laminates, and further, a three-side sealed bag was produced by a die roll filling machine and filled with water The bag breaking strength was measured, and a comprehensive evaluation was performed. The evaluation results are shown in Table 1.

＜酸素透過度の測定＞
実施例１〜８で得られた強密着透明ガスバリア性フィルムを、ＪＩＳ Ｋ−７１２６Ｂ法に準拠して、Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌ社製のＯｘｔｒａｎ２／２０により、３０℃７０％ＲＨ環境の条件で測定した。
＜常態ラミネート強度の測定＞
実施例１〜８の強密着透明ガスバリア性積層体における強密着透明ガスバリア性フィルムと直鎖状低密度ポリエチレンフィルムとの間の密着強度を、ＪＩＳ Ｚ−１７０７に準拠して測定した。測定条件は、試験幅１５ｍｍ、剥離速度３００ｍｍ／ｍｉｎ、剥離角度Ｔ型とした。
＜湿潤ラミネート強度の測定＞
実施例１〜８の強密着透明ガスバリア性積層体における強密着透明ガスバリア性フィルムと直鎖状低密度ポリエチレンフィルムとの間の湿潤時の密着強度を、ＪＩＳ Ｚ−１７０７に準拠し測定した。測定条件は、試験幅１５ｍｍ、剥離速度３００ｍｍ／ｍｉｎ、剥離角度Ｔ型とし、測定は剥離界面を水で湿潤させながら行った。
＜破袋試験＞
実施例１〜８の強密着透明ガスバリア性積層体を用いて、ダイロール充填機により８０×１００ｍｍの三方シール袋を作製し、内容物に水３０ｇを充填した。その後、水が充填された三方シール袋を、水道水中に１日浸漬した後に取り出して破袋するまでの強度を測定した。破袋強度は、三方シール袋を２枚のアクリル板の間に挟み、圧縮速度１０ｍｍ／ｍｉｎにてアクリル板の上より圧縮させ、三方シール袋が破袋したときの強度で評価した。

<Measurement of oxygen permeability>
The strong adhesion transparent gas barrier films obtained in Examples 1 to 8 were measured under the conditions of 30 ° C. and 70% RH environment by OXTRAN 2/20 manufactured by Modern Control in accordance with JIS K-7126B method.
<Measurement of normal laminate strength>
The adhesion strength between the strong adhesion transparent gas barrier film and the linear low density polyethylene film in the strong adhesion transparent gas barrier laminates of Examples 1 to 8 was measured according to JIS Z-1707. The measurement conditions were a test width of 15 mm, a peeling speed of 300 mm / min, and a peeling angle T type.
<Measurement of wet laminate strength>
The wet adhesion strength between the strong adhesion transparent gas barrier film and the linear low density polyethylene film in the strong adhesion transparent gas barrier laminates of Examples 1 to 8 was measured according to JIS Z-1707. The measurement conditions were a test width of 15 mm, a peeling speed of 300 mm / min, and a peeling angle T type, and the measurement was performed while the peeling interface was wetted with water.
<Broken bag test>
Using the strong adhesion transparent gas barrier laminates of Examples 1 to 8, a 80 × 100 mm three-sided seal bag was produced by a die roll filling machine, and the contents were filled with 30 g of water. Then, the strength until the three-side sealed bag filled with water was taken out after being immersed in tap water for one day and broken was measured. The bag breaking strength was evaluated based on the strength when the three-side seal bag was broken after the three-side seal bag was sandwiched between two acrylic plates and compressed from above the acrylic plate at a compression speed of 10 mm / min.

  As can be seen from Table 1, the strong adhesion transparent gas barrier film of the present invention and the strong adhesion transparent gas barrier laminate using the same in Examples 1 to 6 are not only excellent in oxygen permeability, but also normal and wet laminate strength. In addition, the bag-breaking strength when the liquid contents are filled is also high, and has excellent strength properties. From this result, even when applied to packaging for liquid contents or moisture-containing contents, the possibility of bag breakage and delamination problems is extremely low, and a wide range of uses as packaging materials can be expected, and the utility value is very high It turned out to be expensive.

  On the other hand, the strong adhesion transparent gas barrier films of Examples 7 to 8 and the strong adhesion transparent gas barrier laminate using the same were not good in gas barrier properties of the strong adhesion transparent gas barrier film. The strength of the porous laminate, particularly the wet laminate strength, was low. Due to the influence, the bag breaking strength when the liquid content was filled also showed a low value as compared with the strong adhesion transparent gas barrier laminate of the present invention. From this result, when the packaging material using the strong adhesion transparent gas barrier laminates of Examples 7 to 8 is applied to the liquid content and the moisture-containing content, there is a high possibility of causing bag breakage and delamination, It was judged that practically sufficient performance was not obtained.

It is explanatory drawing which shows the general | schematic cross-section structure of the strong_contact | adherence transparent gas barrier film of this invention. It is explanatory drawing which shows the general | schematic cross-section structure of the strong_contact | adherence transparent gas-barrier laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Polyamide-type resin film 2 ... 1st anchor coat layer 3 ... 2nd anchor coat layer 4 ... Deposition thin film layer 5 which consists of inorganic oxides ... Gas barrier coating layer 6 ... Adhesive layer 7 ... Heat-sealable resin layer 10 ... Base film 20 ... Strong adhesion transparent gas barrier film 30 ... Strong adhesion transparent gas barrier laminate

Claims (7)

At least one surface of the polyamide-based resin film is formed of an anchor coat liquid mainly composed of a difunctional isocyanate monomer or an isocyanate compound which is a derivative of an adduct, burette, or isocyanurate type trifunctional monomer. One anchor coat layer, a trifunctional organosilane represented by the general formula R ₁ Si (OR ₂ ) (R ₁ = amino group, isocyanate group, sulfoxide group, epoxy group, R ₂ = alkyl group), a polyol compound, and A transparent vapor-deposited thin film layer made of an inorganic oxide and a gas barrier coating on a second anchor coat layer of a base film in which a second anchor coat layer made of an anchor coat liquid that is a composite with an isocyanate compound is sequentially laminated. Strongly-adherent transparent gas barrier characterized in that layers are sequentially laminated Film.   2. The strong adhesion transparent gas barrier film according to claim 1, wherein the inorganic oxide is any one of aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof. dance   The gas barrier coating layer is mainly composed of a water-soluble polymer, (a) one or more metal alkoxides and hydrolysates thereof, or (b) an aqueous solution or a water / alcohol mixed solution containing at least one of tin chloride. 3. The strong adhesion transparent gas barrier film according to claim 1, comprising a gas barrier coating liquid.   The strong adhesion transparent gas barrier film according to any one of claims 1 to 3, wherein the thickness of the first anchor coat layer and the second anchor coat layer is in the range of 0.005 to 1 µm.   The first anchor coat layer and the second anchor coat layer are formed by sequentially performing a curing treatment at a temperature of 30 to 80 ° C. after thin films made of the anchor coat liquid constituting each of the first anchor coat layer and the second anchor coat layer are laminated. The strong adhesion transparent gas barrier film according to any one of claims 1 to 4.   A strongly adhesive transparent, characterized in that a heat sealable resin layer is provided on the gas barrier coating layer of the strong adhesive transparent gas barrier film according to any one of claims 1 to 5 via an adhesive layer. Gas barrier laminate.   The normal laminate strength at the boundary surface between the gas barrier coating layer and the heat sealable resin layer of the strong adhesion transparent gas barrier film is 5.0 N / 15 mm or more, and the wet laminate strength when water is immersed in the boundary surface is 2. The strongly-adhesive transparent gas barrier laminate according to claim 6, wherein the laminate is 5 N / 15 mm or more.

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