JP2007130865A - High-adhesion gas barrier transparent film and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-adhesion gas barrier transparent film being excellent in transparency and physical strengths, having high gas barrier properties, having high adhesion, especially, wet adhesion, between a base film and a vapor-deposited film, and being not easily broken when used in a bag form and to provide a laminate using the same. <P>SOLUTION: What is provided is: a high-adhesion gas barrier transparent film prepared by using a transparent polyamide film (1) having an easy-adhesion layer (2) as a base film and sequentially laminating a primer layer (3), a vapor-deposited film layer (4), and a gas barrier film layer (5) on the easy-adhesion layer (2); and a laminate using the same. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transparent gas barrier laminate for use in the packaging field of foods, non-foods, pharmaceuticals, etc., and is particularly excellent in transparency and physical strength, has a high gas barrier property, and a polyamide film as a base material. In particular, the present invention relates to a strong adhesion gas barrier transparent film having a high adhesiveness to laminate, particularly an adhesive property when wet, and in which a laminated portion does not easily peel off, and a laminate using the same.

  Generally, polyamide-based films are excellent in mechanical properties, optical properties, toughness, pinhole resistance, bending resistance, and the like, and are widely used mainly for packaging applications. In particular, when films are used for packaging foods, non-foods, pharmaceuticals, etc., gases such as oxygen and water vapor permeate the packaging material in order to suppress alteration of the contents and maintain their functions and properties. It is required to have a gas barrier property that prevents the above. Therefore, conventionally, a packaging material using a metal foil such as an aluminum foil, which is less affected by temperature, humidity and the like, as a gas barrier layer has been generally used.

  However, a packaging material using a metal foil such as an aluminum foil is excellent in gas barrier properties, but the contents cannot be confirmed through the packaging material. When it is discarded after use, it must be treated as an incombustible material. There was a problem that the metal detector could not be used during the inspection.

  Therefore, as a packaging material that has overcome these drawbacks, for example, an inorganic oxide such as silicon oxide, aluminum oxide, and magnesium oxide is formed on a polymer film by a deposition method such as vacuum deposition or sputtering. A film has been developed. These vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foil or the like. Yes. (For example, refer to Patent Document 1 and Patent Document 2.)

  However, even the polyamide-based film suitable for the packaging material described above is rarely used as a vapor deposition film alone as a packaging container or packaging material, and characters, designs, etc. are applied to the vapor deposition film surface as post-processing after vapor deposition. The packaging body is completed through various processes such as printing, bonding with a sealant film, etc., and shape processing of the packaging body such as a container.

  However, a film obtained by simply depositing an inorganic oxide on a polyamide film has a problem in the adhesion between the polyamide film as a base material and the deposited thin film layer, and is bonded to the sealant film using the above-described deposited film. When the contents were filled after bag making, the adhesive strength between the films was not sufficient, and the bags were easily broken.

  In particular, the adhesiveness when wet is weak, and polyamide-based films often have heavy contents such as liquids that require high strength due to their high toughness. It was. For this reason, when depositing an inorganic oxide on a polyamide-based film, a polyamide-based film having an easy-adhesion layer is used for the purpose of improving the adhesion between the polyamide-based film and the deposited thin film, or a primer layer is used. They are stacked. (For example, refer to Patent Document 3).

Prior art documents are shown below.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No. 63-28017 Japanese Patent Laid-Open No. 10-58586

  The present invention is intended to solve such problems of the prior art, is excellent in transparency and physical strength properties, has high gas barrier properties, and adheres between the base film and the deposited thin film layer. It is an object to provide a strong adhesion gas barrier transparent film that has high properties, particularly high wet adhesion, and does not easily break the bag, and a laminate using the same.

  The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 of the present invention uses a transparent polyamide film (1) having an easy-adhesion layer (2) as a base film. The primer layer (3), the vapor-deposited thin film layer (4) made of an inorganic oxide, and the gas barrier coating layer (5) are sequentially laminated on the surface of the easy adhesion layer (2). It is a strong adhesion gas barrier transparent film.

  The invention according to claim 2 of the present invention is the strong adhesion gas barrier transparent film according to claim 1, wherein the primer layer (3) is a composite of a silane wrapping agent or a hydrolyzate thereof, a polyol and an isocyanate compound. It is a strong adhesion gas barrier transparent film characterized by comprising.

  The invention according to claim 3 of the present invention is the strong adhesion gas barrier transparent film according to claim 1 or 2, wherein the silane coupling agent or a hydrolyzate thereof has at least one of a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. It is a strong adhesion gas barrier transparent film characterized by including a reactive functional group.

  The invention according to claim 4 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 3, wherein a reaction catalyst is added to the composite. It is a transparent film.

  The invention according to claim 5 of the present invention is the strong adhesion gas barrier transparent film according to claim 4, wherein the reaction catalyst is a tin compound.

  The invention according to claim 6 of the present invention is the strong adhesion gas barrier transparent film according to claim 5, wherein the tin compound is a tin compound selected from tin chloride, tin oxychloride and tin alkoxide. It is an adhesive gas barrier transparent film.

The invention according to claim 7 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 6, wherein the composite further includes a general formula M (OR) _n (M: metal element). , R: alkyl group such as CH ₃ , C ₂ H ₅ , n: oxidation number of metal element) or a hydrolyzate of the metal alkoxide, or a strongly adherent gas barrier transparent film, It is.

The invention according to claim 8 of the present invention is the strong adhesion gas barrier transparent film according to claim 7, wherein the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si, Al, Ti, Zr or a mixture thereof. It is a strong adhesion gas barrier transparent film characterized by being.

  The invention according to claim 9 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 8, wherein the thickness of the primer layer (3) is in the range of 0.01 to 2 μm. This is a strong adhesion gas barrier transparent film.

  The tenth aspect of the present invention is the strong adhesion gas barrier transparent film according to any one of the first to ninth aspects, wherein the easy-adhesion layer (2) of the base film is composed of an aqueous polyurethane resin and a melamine system. It is a strong adhesion gas barrier transparent film characterized by being a film formed from a crosslinking agent.

  The invention according to claim 11 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 9, wherein the easy-adhesion layer (2) of the base film is formed of a hydrophobic polyester resin. It is a strong adhesion gas barrier transparent film characterized by being a formed film.

  The invention according to claim 12 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 11, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. This is a strong adhesion gas barrier transparent film.

  The invention according to claim 13 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 12, wherein the gas barrier coating layer (5) comprises a water-soluble polymer, and (a) 1 It is a layer formed by applying a coating agent mainly composed of an aqueous solution containing at least one of metal alkoxides and their hydrolyzates or at least one of tin chloride or a water / alcohol mixed solution, followed by drying by heating. It is a strong adhesion gas barrier transparent film.

  The invention according to claim 14 of the present invention is the strong adhesion gas barrier transparent film according to any one of claims 1 to 13, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. This is a strong adhesion gas barrier transparent film.

  The invention according to claim 15 of the present invention is the strong adhesion gas barrier transparent film according to claim 13 or 14, wherein the water-soluble polymer is polyvinyl alcohol.

  The invention according to claim 16 of the present invention is a laminate characterized by being produced using the strong adhesion gas barrier transparent film according to any one of claims 1 to 15.

  The strong adhesion gas barrier transparent film according to the present invention uses a transparent polyamide-based film (1) having an easy adhesion layer (2) as a base film, and a primer layer (3) on the surface of the easy adhesion layer (2). In addition, a vapor-deposited thin film layer (4) and a gas barrier coating layer (5) made of an inorganic oxide are sequentially laminated to provide excellent transparency and physical strength, high gas barrier properties, and a substrate. Since the adhesiveness between the film and the deposited thin film layer, particularly when wet, is high, and the laminated portion does not peel easily, a packaging material that is difficult to break can be obtained. Furthermore, a laminate using the same is applied as a packaging film for foods, pharmaceuticals, precision electronic parts, and the like, and can provide packaging materials with a wide practical range.

  An embodiment of the present invention will be described in detail based on FIG. 1 and FIG.

  FIG. 1 is a side sectional view for explaining a strongly-adhesive gas barrier transparent film (10) and a strongly-adhesive gas barrier laminate (20) using the same according to the present invention, and FIG. 2 is a planer type plasma treatment according to the present invention. FIG.

  As shown in FIG. 1, the layer structure of the strong adhesion gas barrier transparent film (10) showing one embodiment according to the present invention is a transparent polyamide-based film (1) having an easy adhesion layer (2) as a base film, On the surface of the easy adhesion layer (2), a strongly adherent gas barrier transparent film (3) is formed by sequentially laminating a primer layer (3), a vapor-deposited thin film layer (4) made of an inorganic oxide, and a gas barrier coating layer (5) on the surface. 10). Furthermore, the strongly-adhesive gas barrier laminate (20) according to the present invention comprises a heat-sealable resin layer (on the gas-barrier coating layer (5) of the strongly-adhesive gas barrier transparent film (10) via an adhesive layer (6)). 7) is a laminated structure.

  The transparent polyamide film (1) used in the present invention is preferably a transparent film substrate if possible in order to make use of the transparency of the deposited thin film layer (4). The material of the polyamide film is not particularly limited, and homopolyamide, copolyamide, or a mixture thereof can be used.

  Examples of homopolyamides include polycaprolactam (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin lactam (nylon). 12), polyethylenediamine adipamide (nylon 2, 6), polytetramethylene adipamide (nylon 4, 6), polyhexamethylene didipamide (nylon 6, 6), polyhexamiethylene sebacamide (nylon) 6,10), polyhexamethylene decanamide (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), polydecamethylene sebacamide (Nylon 10, 10), polydecamethylene dodecamide (nylon 12, 12), meta And xylenediamine-6 nylon (MXD6).

  Examples of copolyamides include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylenediamine ammonium sebacate copolymer, hexamethylene diammonium adipate / hexamethy Examples include a diammonium sebacate copolymer and a caprolactam / hexamethylene diammonium adipate / hexamytylene diammonium sebacate copolymer. What is necessary is just to select suitably in consideration of the use environment of the strong adhesion gas barrier laminated body (20), the kind of to-be packaged object, workability, economical efficiency, etc.

  Furthermore, in order to impart flexibility to these transparent polyamide-based films (1), a plasticizer such as aromatic sulfonamide, p-hydroxybenzoic acid, or esters is blended, or an elastomer component or lactam having a low elastic modulus. It is also possible to add a kind or the like. Examples of the elastomer component include ionomer resins, modified polyolefin resins, thermoplastic polyurethanes, polyether block amides, polyester block amides, polyether ester amide elastomers, modified acrylic rubbers, and modified ethylene propylene rubbers.

  On the transparent polyamide film (1), a film formed from an aqueous polyurethane resin and a melamine crosslinking agent or a film formed from a hydrophobic polyester resin is formed as an easy adhesion layer (2). Can do.

  First, the easily bonding layer (2) which consists of a film | membrane formed using water-based polyurethane-type resin and a melamine type crosslinking agent is demonstrated in detail.

  Examples of the aqueous polyurethane resin include an ionomer type self-emulsifying polyurethane resin, an ionomer type self-emulsifying polyurethane-polyurea resin, and the like. In order to improve the solvent resistance, it is preferable to use an aromatic component for at least one of both components. Moreover, in order to improve adhesiveness, it is preferable to use what introduce | transduced the hydroxyl group, the carboxyl group, and the amino group into the polymer principal chain or the terminal.

  As the melamine-based cross-linking agent, a melamine methylolated one is used, and a methylol group alkoxylated one is generally used in order to provide reactivity control and storage stability. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Moreover, you may add a crosslinking catalyst as needed. Examples of the crosslinking catalyst include p-toluenesulfonic acid.

  The addition amount of the melamine-based crosslinking agent is preferably 5 to 7 parts by weight with respect to 90 to 100 parts by weight of the aqueous polyurethane resin. If the addition amount of the melamine crosslinking agent is less than 5 parts by weight, the solvent resistance becomes insufficient, and if it is more than 7 parts by weight, the solvent resistance is saturated, which is not economical. Moreover, a crosslinking reaction can be accelerated | stimulated by adding 5 to 7weight% of a crosslinking catalyst with respect to the quantity of a crosslinking agent as needed.

  Various known additives such as an antistatic agent and a slip agent can be added to the easy-adhesion coating solution in the present invention, as necessary, within a range that does not affect the adhesiveness. Further, an antifoaming agent and a surfactant can be added in order to improve coatability.

  The thickness of the easy-adhesion layer (2) is preferably 0.01 to 0.1 μm after the film is stretched by providing the easy-adhesion layer (2) on the transparent polyamide film (1). Preferably it is 0.02-0.08 micrometer. When the thickness of the film is less than 0.02 μm, sufficient adhesion cannot be obtained, and even if it is thicker than 0.1 μm, the performance is saturated. Absent.

  Coating method of the film is not particularly limited, for example, gravure roll method, reverse roll method, air knife method, reverse gravure method, Mayer bar method, inverse roll method, or a combination of these, various spray methods Etc. can be adopted. Moreover, a corona treatment apparatus etc. can be installed between a longitudinal stretch machine and a coater, and the wet tension of the film after longitudinal stretch can be adjusted.

  Next, the easily bonding layer (2) which consists of a film | membrane formed using hydrophobic polyester-type resin is demonstrated in detail.

  Examples of the hydrophobic polyester resin include a crosslinkable polyester resin composed of a polyester resin and a crosslinkable resin. The polyester resin is a crystalline or non-crystalline polyester resin, and is a polyester resin having a crosslinkable group in order to perform a crosslinking reaction with the crosslinked resin.

The polyester resin is a polyester resin prepared by polycondensation of an acid component such as dicarboxylic acid or tricarboxylic acid and a glycol component using a known method. Examples of such an acid component include terephthalic acid, isophthalic acid, adipic acid, trimellitic acid and the like, but are not particularly limited thereto. Examples of the glycol component include, but are not limited to, ethylene glycol, neopentyl glycol, butanediol, and ethylene glycol modified bisphenol A.

  Examples of the crosslinkable polyester resin include a graft polymer having an acrylic acid group, which is obtained by a graft reaction between the crystalline or non-crystalline polyester resin and a monomer or oligomer having an acrylic acid group. be able to. Further, the crystalline or non-crystalline polyester resin and, for example, oxazoline compound, polyfunctional epoxy compound, silane compound, alkylated phenol compound, phenol formaldehyde resin, urea, melamine, benzoguanamine, etc. and formaldehyde Cross-links such as amino resins such as alkyl ether compounds comprising these addition polymers and alcohols having 1 to 6 carbon atoms, polyfunctional isocyanate compounds, block isocyanate compounds, polyfunctional aziridine compounds, etc. It is a reaction product with the agent.

  Furthermore, the water-adhesive easy-adhesion layer (2) based on a polyester resin is a self-crosslinkable polyester system in which at least one polymerizable unsaturated monomer is graft-polymerized on a hydrophobic polyester resin. The resin composition which has a graft copolymer as a main component can be illustrated. The hydrophobic polyester resin is a polyester-based resin that is essentially water-insoluble and does not disperse or dissolve in water by itself.

  The dicarboxylic acid component of the hydrophobic polyester resin is preferably an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, a dicarboxylic acid having a polymerizable unsaturated double bond, or the like. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, and biphenyl dicarboxylic acid. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof. Dicarboxylic acids having a polymerizable unsaturated double bond include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid and other α, β-unsaturated dicarboxylic acids; 2,5-norbornene dicarboxylic acid anhydride, Examples include alicyclic dicarboxylic acids such as tetrahydrophthalic anhydride. Among these, fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid are preferable from the viewpoint of polymerizability.

  Examples of the glycol component of the hydrophobic polyester resin include aliphatic glycol, alicyclic glycol, and ether bond-containing glycol. Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, Examples include 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2-ethyl-2-butylpropanediol. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol. Can be mentioned. Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols [for example, 2,2-bis (4-hydroxyethoxyphenyl) propane etc.] and the like.

The hydrophobic polyester resin can also contain a tri- or higher functional polycarboxylic acid and / or polyol as a copolymerization component. Examples of the tri- or higher functional polycarboxylic acid include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (Anhydro trimellitate) and the like. Examples of the tri- or higher functional polyol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

  The molecular weight of the hydrophobic polyester resin is preferably in the range of less than 50000 in terms of weight average molecular weight. If the molecular weight exceeds 50000, problems such as gelation during polymerization may occur.

  Examples of the polymerizable unsaturated monomer graft-polymerized on the hydrophobic polyester resin include fumaric acid; monoesters or diesters of fumaric acid such as monoethyl fumarate, diethyl fumarate, dibutyl fumarate; and maleic acid. Its anhydride; monoester or diester of maleic acid such as monoethyl maleate, diethyl maleate, dibutyl maleate; itaconic acid and its anhydride; monoester or diester of itaconic acid; maleimide such as phenylmaleimide; styrene , Α-methylstyrene, t-butylstyrene, chloromethylstyrene, vinyltoluene, divinylbenzene, and other styrene derivatives and acrylic polymerizable monomers such as alkyl (meth) acrylate (alkyl groups include methyl, ethyl Group, n-propi Group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Hydroxy group-containing (meth) acrylic monomers such as 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide Amide group-containing (meth) acrylic monomers such as N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide; Amino group-containing (meth) acrylic monomers such as ethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; Epoxy group-containing (meth) acrylic monomers such as glycidyl acrylate and glycidyl methacrylate; Acrylic acid, methacrylic acid and the like Carboxyl group-containing (meth) acrylic monomers and the like such as sodium salts (sodium salt, potassium acid, ammonium salt). The said monomer can be copolymerized using 1 type, or 2 or more types. Among these, styrene and maleic anhydride are preferable.

  When this graft copolymer is used as a water-dispersed resin, the weight average molecular weight of the polymer component of the polymerizable unsaturated monomer that is a branch polymer in the graft copolymer is preferably 500 to 50,000. In general, it is difficult to control the weight average molecular weight of the polymer component to 500 or less, the graft efficiency is lowered, and there is a tendency that hydrophilic groups are not sufficiently imparted to the hydrophobic polyester resin. In addition, the polymer component of the polymerizable unsaturated monomer in the graft copolymer forms a hydrated layer of dispersed particles, but in order to obtain a stable dispersion by providing a hydrated layer of sufficient thickness. The polymer component desirably has a weight average molecular weight of 500 or more. Further, the upper limit of the weight average molecular weight of the polymer component is preferably 50000 in view of polymerizability in solution polymerization. The molecular weight within this range is controlled by using a polymerization initiator in an appropriate amount, a monomer dropping time, a polymerization time, a reaction solvent, a monomer composition, or a chain transfer agent or a polymerization inhibitor as appropriate. Can be done.

  A high water resistance can be imparted to the easy-adhesion layer (2) by further blending and curing the crosslinked resin in the resin composition mainly composed of the polyester-based resin thus formed. As the crosslinked resin, those described above can be used.

  The easy-adhesion layer (2) may further contain additives such as various surfactants, antistatic agents, inorganic lubricants, organic lubricants, and ultraviolet absorbers, as long as the effects of the present invention are not impaired.

The easy-adhesion layer (2) is formed by using an aqueous dispersion mainly composed of the above-described polyester resin.
It is performed by applying and drying on an unstretched or uniaxially stretched transparent polyamide film (1). The solid content of the polyester resin in the dispersion is usually 1% by weight to 50% by weight.

As a coating method, known methods such as a gravure coating method, a reverse gravure coating method, a die coating method, a bar coating method, and a dip coating method can be employed. The coating amount is 0.005 to 10 g / m ² as a solid content. When the coating amount is less than 0.005 g / m ^2, sufficient adhesion strength between the polyamide film (1) is not obtained. When it exceeds 10 g / m ² , blocking occurs and there is a practical problem.

  There are no particular restrictions on the drying conditions after coating, but conditions that increase the amount of heat within a range in which the polyamide-based film (1) does not undergo thermal degradation are preferred. Specifically, it is 80 to 250 ° C. However, by extending the drying time, sufficient self-crosslinking property is exhibited even at a relatively low temperature. When the coating liquid is applied and dried on the unstretched or uniaxially stretched polyamide-based film (1), when the film (1) is stretched uniaxially or more, the drying temperature after coating affects the subsequent stretching. In the case of the polyamide-based film (1), the film is stretched by setting the moisture content of the coating to 2% or less, and then heat-fixed at 200 ° C. or more to strengthen the coating. Thus, the adhesion between the easy-adhesion layer and the polyamide film (1) is greatly improved. If the moisture content exceeds 2%, although depending on the drying temperature, crystallization is likely to occur during the transverse stretching step, and planarity may be deteriorated and stretchability may be impaired.

  As described above, the thickness of the base film provided with the easy-adhesion layer (2) on the transparent polyamide-based film (1) is 10 to 10 in consideration of vapor deposition processability and mechanical characteristics as a packaging material. The one with 100 μm is used.

  In order to improve the adhesion between the easy adhesion layer (2) on the transparent polyamide film (1) and the deposited thin film layer (4) made of an inorganic oxide, a primer layer (3) is provided. The purpose of this layer (3) is to increase the adhesion between the base film and the vapor-deposited thin film layer (4) made of an inorganic oxide, and to prevent bag breakage after bag making.

  As a result of intensive studies, it is necessary to use a composite of a silane coupling agent or a hydrolyzate thereof, a polyol, an isocyanate compound, and the like that can be used as a primer resin to achieve the above object.

  As an example of the silane coupling agent, a silane coupling agent containing an arbitrary organic functional group can be used, for example, ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyl. Use one or more of silane coupling agents such as trimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or hydrolysates thereof. Can do.

Further, among these silane coupling agents, those having a functional group that reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing an isocyanate group such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, those containing a mercapto group such as γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, Some include amino groups such as γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, and γ-phenylaminopropyltrimethoxysilane. Furthermore, those containing an epoxy group such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
A silane coupling agent such as vinyltrimethoxysilane or vinyl (β-methoxyethoxy) silane may be added with alcohol or the like to add a hydroxyl group or the like, and one or more of these may be used. These silane coupling agents have a silane cup containing a functional group in which an organic functional group present at one end exhibits an interaction in a composite composed of a polyol and an isocyanate compound, or reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. A stronger primer layer (3) is formed by providing a covalent bond by using a ring agent, and a silanol group formed by hydrolysis of an alkoxy group or the like at the other end is a metal in an inorganic oxide or an inorganic oxide. It exhibits high adhesion with inorganic oxides by strong interaction with a highly active hydroxyl group or the like on the surface, and the desired physical properties can be obtained. Therefore, you may use what hydrolyzed the said silane coupling agent with the metal alkoxide. In addition, there is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group, etc., and these alkoxy groups, chloro groups, acetoxy groups, etc. are hydrolyzed to form silanol groups. Can be used in this composite.

  The polyol has two or more hydroxyl groups at the polymer terminal and is reacted with an isocyanate group in an isocyanate compound to be added later. Among these, an acrylic polyol which is a polyol obtained by polymerizing an acrylic acid derivative monomer or a polyol obtained by copolymerizing with an acrylic acid derivative monomer and other monomers is particularly preferable. Among these, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxylbutyl methacrylate alone, and acrylic polyols obtained by copolymerizing with other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

  The mixing ratio of the polyol and the silane coupling agent is preferably in the range of 1/1 to 1000/1 in terms of weight ratio, more preferably in the range of 2/1 to 100/1. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted. For example, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as methyl ethyl ketone, A mixture of aromatic hydrocarbons such as toluene and xylene alone and arbitrarily can be used. However, since an aqueous solution such as hydrochloric acid may be used to hydrolyze the silane coupling agent, it is preferable to use a solvent in which isopropyl alcohol or the like and ethyl acetate that is a polar solvent are arbitrarily mixed as a cosolvent.

Further, a reaction catalyst may be added in order to accelerate the reaction when the silane coupling agent and polyol are blended. The catalyst to be added is a tin compound such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ), tin axoxide in terms of reactivity and polymerization stability. Is preferred. If the addition amount is too small or too large, the catalytic effect cannot be obtained, and therefore it is preferably in the range of 1/10 to 1/10000 in terms of molar ratio with respect to the trifunctional organosilane, more preferably 1 / 100 to 1/2000.

The isocyanate compound to be mixed is added in order to enhance adhesion between the base film and the inorganic oxide layer by a urethane bond formed by reacting with a polyol, and mainly acts as a crosslinking agent or a curing agent. In order to achieve this, as isocyanate compounds, monomers such as aromatic tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI), and the like, These polymers and derivatives are used, and these can be used alone or in combination of two or more.

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

Furthermore, in order to improve the liquid stability during the preparation of the above mixture, a metal alkoxide or a hydrolyzate thereof may be added. The metal alkoxide is a general formula M (OR) _n (M: metal element, R: CH) such as tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), tripropoxy aluminum (Al (OC ₃ H ₇ ) ₃ ), etc. ₃ or an alkyl group represented by a general formula C _n H _{2n + 1} such as C ₂ H _5, or a hydrolyzate thereof. Of these, tetraethoxysilane, tripropoxyaluminum, or a mixture of both is preferable because it is relatively stable in an aqueous solvent. The metal alkoxide hydrolyzate may be hydrolyzed together with the silane coupling agent, or may be added after adding an acid alone.

  The composite coating layer can be obtained by directly or previously hydrolyzing such a silane coupling agent, or by hydrolyzing with a metal alkoxide (even if the above-mentioned reaction catalyst is added together) Can be mixed with polyol or isocyanate compound to prepare a composite solution, or silane coupling agent and polyol are mixed in advance in a solvent (at this time, the above-mentioned reaction catalyst and metal alkoxide are added together) (It does not matter if it is one way) Hydrolyzed reaction, or just a mixture of silane coupling agent and polyol (At this time, it is also possible to add the above-mentioned reaction catalyst and metal alkoxide together) In this, an isocyanate compound is added to prepare a composite liquid, which is then coated on a substrate.

  Various additives such as tertiary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, quaternary phosphonium salts and other curing accelerators, phenols, sulfurs, phosphites It is also possible to add an antioxidant, a leveling agent, a flow regulator, a catalyst, a crosslinking reaction accelerator, a filler, and the like.

  Although the thickness of this primer layer (3) will not be specifically limited if a coating film can be formed uniformly, Generally it is preferable that it is the range of 0.01-2 micrometers. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be lowered. On the other hand, when the thickness exceeds 2 μm, the coating film cannot be kept flexible because it is thick, and the coating film may be cracked due to external factors, which is not preferable. Particularly preferred is a range of 0.03 to 0.5 μm.

  As a method for forming the primer layer (3), for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating is used. be able to. About drying conditions, generally used conditions may be used. Further, in order to promote the reaction, it is possible to leave it in a high temperature aging chamber for several days.

Next, the vapor-deposited thin film layer (4) made of inorganic oxide is made of aluminum oxide, silicon oxide, magnesium oxide, tin oxide, or a mixture thereof, and has transparency and gas barrier properties such as oxygen and water vapor. If it is. Among them, aluminum oxide and silicon oxide are particularly preferable. However, the vapor-deposited thin film layer (4) of the present invention is not limited to the inorganic oxide described above, and any material that meets the above conditions can be used.

  The optimum thickness of the vapor-deposited thin film layer (4) made of the inorganic oxide varies depending on the type and configuration of the inorganic compound used, but is generally within the range of 5 to 300 nm, and the value is appropriately selected. Is done. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. On the other hand, when the film thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked due to external factors such as bending and pulling after the film formation. Preferably, it exists in the range of 10-150 nm.

  There are various methods for forming the vapor-deposited thin film layer (4) made of the inorganic oxide on the primer layer (3), and it can be formed by a normal vacuum vapor deposition method. A method, an ion plating method, a plasma vapor deposition method (CVD), or the like can also be used. However, considering productivity, the vacuum deposition method is the best at present. As the heating means of the vacuum evaporation apparatus by the vacuum evaporation method, an electron beam heating method, a resistance heating method, and an induction heating method are preferable. In order to improve the adhesion between the thin film and the base film and the denseness of the thin film, a plasma assist method or An ion beam assist method can also be used. In addition, in order to increase the transparency of the deposited film, it is possible to carry out reactive deposition by blowing oxygen gas or the like during deposition.

  The said gas barrier coating layer (5) is provided on the vapor deposition thin film layer (4) which consists of an inorganic oxide, in order to provide high gas barrier property like aluminum foil by required quality.

  The gas barrier coating layer (5) is mainly composed of an aqueous solution or a water / alcohol mixed solution containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates or (b) tin chloride. It consists of a coating agent. Mineralize a solution in which water-soluble polymer and tin chloride are dissolved in an aqueous (water or water / alcohol mixed) solvent, or a solution in which metal alkoxide has been directly or previously hydrolyzed. It is formed by coating and heating and drying on a vapor-deposited thin film layer (4) made of an oxide. Each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer used in the coating agent in the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, gas barrier properties are most excellent when polyvinyl alcohol (hereinafter referred to as PVA) is used as the coating agent of the laminate of the present invention. The PVA here is generally obtained by saponifying polyvinyl acetate, and includes from so-called partially saponified PVA in which several dozen percent of acetate groups remain to complete PVA in which only several percent of acetate groups remain. There is no particular limitation.

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

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

Each of the above-mentioned components can be added to the coating agent alone or in combination, and an isocyanate compound, a silane coupling agent, or a dispersant, a stabilizer, and a viscosity adjustment as long as the gas barrier properties of the coating agent are not impaired. Known additives such as coloring agents and coloring agents can be added.

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

  For the coating method of the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, a spray method and the like can be used. The thickness of the coating film varies depending on the type of coating agent and the processing conditions, but it is sufficient that the thickness after drying is 0.01 μm or more. However, if the thickness is 50 μm or more, the film is likely to crack. A range of ˜50 μm is preferred.

  Furthermore, other layers can be laminated on the vapor-deposited thin film layer (4) or the gas barrier coating layer (5) made of the inorganic oxide. For example, a printing layer, an intermediate layer, a heat seal layer, and the like. The printed layer is formed for practical use as a packaging bag, etc., and various pigments are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, rubber and vinyl chloride. , A layer composed of an ink to which additives such as extender pigments, plasticizers, desiccants, stabilizers and the like are added, and characters, patterns, etc. are formed. As a formation method, for example, a known printing method such as a gravure printing method, a silk screen printing method, or a flexographic printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating can be used. The thickness may be 0.1 to 2.0 μm.

  By laminating the heat-sealable resin layer (7) via the adhesive layer (6) on the surface of the gas-barrier coating layer (5) of the strongly-adhesive gas barrier transparent film (10) having the above-described configuration, A laminate (20) can be obtained.

As the adhesive layer (6) used in the present invention, a general-purpose laminating adhesive can be used. For example, poly (ester) urethane, polyester, polyamide, epoxy, poly (meth) acryl, polyethyleneimine, ethylene- (meth) acrylic, polyvinyl acetate, (modified) polyolefin, polybutadiene (No) solvent type, water-based type, and hot melt type adhesives mainly composed of a wax type, wax type, casein type, and the like can be used. 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. The coating thickness is preferably about 0.1 to 8 g / m ² (dry state).

  The heat-sealable resin layer (7) used in the present invention is provided as a seal layer when forming a bag-like package or the like, and particularly if it melts by heat and can be fused to each other. It is not limited. For example, 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 Polymers and saponified products thereof, polycarbonate resins, polyacrylonitrile resins, nitrocellulose, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers and their metal cross-linked products, polylactic acid Biodegradable resins such as resin and other known resins can be arbitrarily used. The thickness may be determined according to the purpose, and is generally in the range of 10 to 200 μm.

  As a method of laminating the heat-sealable resin layer (7) on the strong adhesion gas barrier transparent film (10), other known laminating methods such as a dry laminating method, a non-solvent laminating method, an extrusion laminating method and the like can be used. Further, in the strong adhesion gas barrier laminate (20), a printing layer (not shown) or other base material is formed on the gas barrier coating layer (5) of the strong adhesion gas barrier transparent film (10) according to the use and demand. After laminating a film or the like, a heat-sealable resin layer (7) can be laminated and used for a desired packaging material.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these.

<Preparation of primer layer composite solution A>
In a diluting solvent, 2- (epoxycyclohexyl) ethyltrimethylsilane (hereinafter abbreviated as EETMS) and acrylic polyol are weighed and mixed in an amount of 5.0 times (weight ratio) with respect to EETMS, and tin chloride (SnCl ₂ ) as a catalyst. / Methanol solution (prepared to 0.003 mol / g) is added to EETMS to 1/135 mol and stirred. Next, a mixed solution obtained by diluting a mixed solution of triisyl isocyanate (hereinafter abbreviated as TDI) as an isocyanate compound so that NCO groups are equivalent to OH groups of the acrylic polyol to an arbitrary concentration is referred to as a composite solution A.

<Preparation of primer layer composite solution B>
In a diluting solvent, 9 parts by weight of acrylic polyol and 1 part by weight of polyester polyol are weighed and mixed and stirred with respect to 1 part by weight of γ-isocyanatopropyltrimethylsilane. Next, a mixed solution obtained by diluting a mixed solution in which TDI is added as an isocyanate compound so that NCO groups are equivalent to OH groups of acrylic polyol and polyester polyol to an arbitrary concentration is referred to as composite solution B.

<Example 1>
A biaxially stretched nylon 6 having a thickness of 15 μm is used as the transparent polyamide film (1), an easy adhesion layer (2) is provided on the film (1), and a primer layer is provided on the surface of the easy adhesion layer (2). As (3), the composite solution A was formed to a thickness of 0.2 μm by the gravure coating method. Next, a vapor deposition thin film layer made of an inorganic oxide is formed by evaporating metal aluminum on the primer layer (3) by a vacuum vapor deposition apparatus using an electron beam heating method, introducing oxygen gas therein, and vapor-depositing aluminum oxide having a thickness of 20 nm. (4) was formed. Further, a coating agent having the following composition was applied thereon with a bar coater and dried with a dryer at 120 ° C. for 1 minute to form a gas barrier coating layer (5) having a thickness of 0.3 μm. The strong adhesion gas barrier transparent film of the present invention (10) was obtained.

  Here, the easy-adhesion layer (2) of the transparent polyamide-based film as the base film is formed by coating a liquid mixture of urethane-based resin emulsion and melamine-based crosslinking agent with a hot air dryer at 70 ° C. It was obtained by drying the moisture.

The gas barrier coating solution for forming the gas barrier coating layer (5) was prepared by adding 89 g of hydrochloric acid (0.1N) to 10 g of tetraethoxysilane, stirring for 30 minutes, and hydrolyzing to a solid content of 3 wt% (SiO 2 ₂ conversion) and a 3 wt% water / isopropyl alcohol solution (water: isopropyl alcohol = 90: 10 weight ratio) of polyvinyl alcohol were mixed to obtain a gas barrier coating solution.

Furthermore, a polyurethane adhesive (A525, manufactured by Mitsui Takeda Chemical Co., Ltd.) is used on the gas barrier coating layer (5) surface of the strong adhesion gas barrier transparent film (10).
A heat-sealable resin layer (7) made of a linear low-density polyethylene film (TUX-FCS manufactured by Tosero Co., Ltd.) having a thickness of 50 μm is formed on the adhesive layer (6) having 5 g / m ² by dry lamination. After the lamination, curing was carried out at 40 ° C. for 4 days to obtain a strongly adhered gas barrier laminate (20) of the present invention.

<Example 2>
In Example 1, a strongly adhered gas barrier laminate (20) of the present invention was obtained in the same manner as in Example 1 except that the composite solution B was used as the primer layer (3).

<Example 3>
In Example 1, the strong adhesion gas barrier laminated body (20) of this invention was obtained like Example 1 except having used hydrophobic polyester-type resin as an easily bonding layer (2).

<Example 4>
In Example 3, a strongly adhered gas barrier laminate (20) of the present invention was obtained in the same manner as in Example 3 except that the composite solution B was used as the primer layer (3).

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
A strong adhesion gas barrier laminate (20) was obtained in the same manner as in Example 1 except that the transparent polyamide film (1) subjected to corona treatment without providing the easy-adhesion layer (2) was used. .

<Comparative example 2>
In Example 1, a strongly adhered gas barrier laminate (20) was obtained in the same manner as in Example 1 except that the primer layer (3) was not provided.

<Comparative Example 3>
In Example 1, the primer layer (3) is not provided, but instead, a pretreatment by RIE using a planar type plasma (32) in which a voltage is applied from the cooling drum (33) side as shown in FIG. A strongly adhered gas barrier laminate (20) was obtained in the same manner as in Example 1 except that the base film (34) was applied. At this time, a high frequency power source with a frequency of 13.56 MHz was used for the electrode (31), and an argon / oxygen mixed gas was used for the processing gas. The self-bias value of the plasma (32) at this time was 600V.

<Comparative example 4>
In Example 3, a strongly adhered gas barrier laminate (20) was obtained in the same manner as in Example 3 except that the transparent polyamide film (1) subjected to corona treatment without providing the easy adhesion layer (2) was used. .

<Comparative Example 5>
In Example 3, a strongly bonded gas barrier laminate (20) was obtained in the same manner as in Example 3 except that the primer layer (3) was not provided.

<Comparative Example 6>
In Example 3, the primer layer (3) is not provided, and instead, a pretreatment by RIE using a planar type plasma (32) in which a voltage is applied from the cooling drum (33) side as shown in FIG. A strongly adhered gas barrier laminate (20) was obtained in the same manner as in Example 3 except that the transparent polyamide-based film (34) was applied. At this time, the frequency of the electrode (31) is 13.56.
A high frequency power source of MHz was used, and an argon / oxygen mixed gas was used as a processing gas. The self-bias value of the plasma (32) at this time was 600V.

<Evaluation>
For the tightly bonded gas barrier laminates (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6, oxygen permeability measurement, water vapor permeability measurement, wet laminate strength measurement, pressure strength test, and bending pinhole test are as follows. The measurement / test method shown in FIG. The evaluation results are shown in Table 1.

<Measurement of oxygen permeability>
The strong adhesion gas barrier laminates (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 were subjected to 30 ° C. and 70% RH using Oxtran 2/20 manufactured by Modern Control in accordance with JIS K-7129B method. Measurements were performed under environmental conditions.

<Measurement of water vapor transmission rate>
The strong adhesion gas barrier laminates (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 were subjected to 40 ° C. and 90% RH by Oxtran 3/31 manufactured by Modern Control in accordance with JIS K-7129B method. Measurements were performed under environmental conditions.

<Measurement of wet laminate strength>
Between the heat-adhesive gas barrier transparent film (10) of the strong adhesion gas barrier laminate (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 and the heat-sealable resin layer (7) made of linear low-density polyethylene The adhesion strength of was measured according to JIS Z-1707. Measurement conditions were such that the initial strength was measured with a test width of 15 mm, a peeling speed of 300 mm / min, and a peeling angle T type. The measurement was performed while the peeling interface was wetted with water.

<Pressure strength test>
Using the strong adhesion gas barrier laminate (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6, a 100 × 100 mm four-way seal pouch was prepared, and 40 g of distilled water was filled as the contents. After being immersed in water for 1 day, it was wiped lightly, and a load of up to 500 kg was applied at a pressing speed of 100 mm / min. The maximum pressure strength at that time was measured.

<Bending pinhole test>
The number of pinholes after the strong adhesion gas barrier laminate (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6 was bent 2000 times at 25 ° C. using a gelbo flex tester was checked.

Table 1 shows the results of the oxygen permeability, water vapor permeability, wet laminate strength, pressure strength, and bending pinhole test of the strong adhesion gas barrier laminates (20) obtained in Examples 1 to 4 and Comparative Examples 1 to 6. It is the table | surface which showed.

  From Table 1, the strong adhesion gas barrier laminate (20) of the present invention in Examples 1 to 4 was excellent in wet laminate strength and excellent in oxygen and water vapor permeability. In addition, even when the transparent polyamide film (1) is applied to a liquid content that is often used, the pressure resistance is excellent, so there is little possibility of the problem of bag breakage, the number of pinholes in the bent pinhole test is small, and the transparent polyamide The result which can satisfy the performance as a laminated body using a system film (1) was obtained.

  On the other hand, the strong adhesion gas barrier laminates (20) of Comparative Examples 1 to 6 all had low wet laminate strength and low pressure strength. Satisfactory practical performance could not be obtained when applied to liquid contents.

It is a sectional side view explaining the strong_contact | adherence gas barrier transparent film concerning this invention, and the strong_contact | adherence gas barrier laminated body using the same. It is a schematic diagram at the time of performing the planar type plasma processing which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent polyamide-type film 2 ... Easy-adhesion layer 3 ... Primer layer 4 ... Deposition thin film layer which consists of inorganic oxides 5 ... Gas-barrier coating layer 6 ... Adhesive layer 7. ··· Heat-sealable resin layer 10 ··· Strong adhesion gas barrier transparent film 20 ··· Strong adhesion gas barrier laminate 31 ··· Electrode 32 ··· Plasma 33 ··· Cooling drum 34 ··· Base film

Claims (16)

  A transparent polyamide-based film having an easy-adhesion layer is used as a base film, and a primer layer, a vapor-deposited thin film layer made of an inorganic oxide, and a gas barrier coating layer are sequentially laminated on the surface of the easy-adhesion layer. Strong adhesion gas barrier transparent film.   The strong adhesion gas barrier transparent film according to claim 1, wherein the primer layer comprises a silane wrapping agent or a hydrolyzate thereof, and a composite of a polyol and an isocyanate compound.   The strong adhesion gas barrier transparent film according to claim 1 or 2, wherein the silane coupling agent or a hydrolyzate thereof includes a functional group that reacts with at least one of a hydroxyl group of a polyol and an isocyanate group of an isocyanate compound.   The strong adhesion gas barrier transparent film according to any one of claims 1 to 3, wherein a reaction catalyst is added to the composite.   The strong adhesion gas barrier transparent film according to claim 4, wherein the reaction catalyst is a tin compound.   6. The strong adhesion gas barrier transparent film according to claim 5, wherein the tin compound is a tin compound selected from tin chloride, tin oxychloride and tin alkoxide. In the composite, a metal alkoxide represented by the general formula M (OR) _n (M: metal element, R: alkyl group such as CH ₃ , C ₂ H ₅ , n: oxidation number of metal element) or The strong adhesion gas barrier transparent film according to any one of claims 1 to 6, wherein a hydrolyzate of the metal alkoxide is added.   8. The tightly adhered gas barrier transparent film according to claim 7, wherein the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si, Al, Ti, Zr or a mixture thereof.   The strong adhesion gas barrier transparent film according to any one of claims 1 to 8, wherein the primer layer has a thickness in a range of 0.01 to 2 µm.   The strong adhesion gas barrier transparent film according to any one of claims 1 to 9, wherein the easily adhesive layer of the base film is a film formed of an aqueous polyurethane resin and a melamine crosslinking agent.   The strong adhesion gas barrier transparent film according to any one of claims 1 to 9, wherein the easily adhesive layer of the base film is a film formed of a hydrophobic polyester resin.   The strong adhesion gas barrier transparent film according to any one of claims 1 to 11, wherein the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof.   The gas barrier coating layer is mainly composed of an aqueous solution or a water / alcohol mixed solution containing at least one of a water-soluble polymer and (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride. The strong adhesion gas barrier transparent film according to any one of claims 1 to 12, which is a layer formed by applying a coating agent and drying by heating.   14. The strong adhesion gas barrier transparent film according to claim 13, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   15. The strong adhesion gas barrier transparent film according to claim 13 or 14, wherein the water-soluble polymer is polyvinyl alcohol.   A laminate produced using the strong adhesion gas barrier transparent film according to any one of claims 1 to 15.