Gas-barrier laminated film

Gas barrier laminated film

GAS-BARRIER LAMINATED FILM

The present invention relates to a gas-barrier laminated film with transparency and superior gas barrier properties against water vapor, oxygen, etc., suitable for use as packaging films for foods and pharmaceuticals. More specifically, it relates to a gas-barrier laminated film that can obtain good gas barrier properties and adhesion (laminated strength) even after retort treatment.

Previously, it is well known that a metal film such as aluminum or an inorganic oxide film such as silicon oxide or aluminum oxide is layered on the surface of a plastic film as a gas barrier film. Among them, thin films obtained by laminating inorganic oxides such as silica, alumina, and mixtures of these are transparent and the contents can be confirmed, so they are widely used in food applications.

However, these inorganic thin films are prone to pinholes or cracks during the thin film formation step, and during the processing steps, the inorganic thin film layer will crack and cracks, so that the originally expected sufficient gas barrier properties cannot be obtained. Therefore, in order to improve these shortcomings, an attempt has been made to provide a gas barrier layer on the inorganic thin film. With the gas barrier film of this method, a gas barrier film in which a resin layer containing an inorganic layered compound of a specific particle size and aspect ratio is coated on an inorganic film has been disclosed (for example, Patent Document 1).

In addition, there are also many proposals for coating the surface of the plastic film with a resin composition with high gas barrier properties. In the resin used for these films In terms of composition, there is also known a method of dispersing flat-shaped inorganic substances such as inorganic layered compounds in a resin as a method to improve gas barrier properties. A barrier coating agent composed of an ethylene-vinyl alcohol-based copolymer, a water-soluble zirconium-based crosslinking agent, and an inorganic layered compound (for example, Patent Document 2 of the invention).

However, even if these methods are adopted, although the characteristics of retort or high humidity can be improved, it is still impossible to obtain a gas barrier film that can meet the gas barrier properties, laminate strength, and stable quality after sterilization. .

[Prior Technical Literature]

[Invention Patent Literature]

[Invention Patent Document 1] Patent No. 3681426

[Invention Patent Document 2] Japanese Patent Laid-Open No. 2008-297527

<p>The present invention is achieved in view of the technical problems of the prior art as described above. That is, the object of the present invention is to provide an excellent gas barrier property and interlayer density that can be used for packaging applications of various foods, medicines, industrial products, solar cells, electronic paper, organic EL elements, semiconductor elements, etc. Adhesive gas barrier laminated film. In particular, it provides a gas-barrier laminated film that has little reduction in gas barrier properties even after sterilization treatment, and does not cause interlayer peeling.</p>

<p>The gas barrier laminated film of the present invention, which can solve the above-mentioned technical problems, is characterized in that on at least one surface of the plastic film, an inorganic film layer and a gas barrier resin composition layer are interposed or not interposed by other layers The layers are sequentially laminated, and the gas barrier resin composition layer is formed of a gas barrier resin composed of an ethylene-vinyl alcohol copolymer, and a gas barrier resin composition composed of an inorganic layered compound and additives, And the content of the inorganic layered compound in the gas barrier resin composition is 0.1% by mass to 9.0% by mass, the additive is a coupling agent and/or a crosslinking agent, and the thickness of the gas barrier resin composition layer is 0.05 μm to 0.5μm.</p><p>As described above, the inorganic layered compound is suitable for use of smectite. As described above, the inorganic thin film layer preferably contains at least an inorganic oxide.</p><p>If a coupling agent is used as the additive as described above, the coupling agent is preferably a silane coupling agent having at least one organic functional group. When a crosslinking agent is used as the additive, the crosslinking agent is preferably a crosslinking agent containing a hydrogen bonding group. In this case, the total content of the additives (coupling agent and/or crosslinking agent) in the gas barrier resin composition as described above is preferably 0.3% by mass to 20% by mass.</p><p>It is also a preferable mode to have an anchor coat layer with a thickness of 0.05 μm to 0.5 μm between the aforementioned inorganic thin film layer and the aforementioned gas barrier resin composition layer. The resin composition of the thickening coating agent used to form the thickening coating layer preferably contains a silane coupling agent having at least one organic functional group. In addition, when used to form the viscosity-increasing coating In the resin composition of the thickening coating agent of the layer, the addition amount of the silane coupling agent is preferably 0.1% by mass to 10% by mass.</p>

<p>According to the present invention, it is possible to obtain a gas-barrier laminated film with superior gas barrier properties against oxygen and water vapor, high interlayer adhesion, and superior laminate strength. In particular, it is a laminated film with gas barrier properties that can obtain gas barrier properties even if sterilization treatment is applied, the reduction of layer indirect stress is small, and the practicality of the gas barrier properties is high for various purposes. In addition, a gas barrier laminated film with superior production stability and homogeneous characteristics can also be easily obtained.</p>

[Best embodiment of the present invention]

The gas barrier laminated film of the present invention is formed on at least one surface of a plastic film, and an inorganic film layer and a gas barrier resin composition layer are laminated in sequence with or without other layers. In the following, the gas barrier multilayer film of the present invention is divided into layers to explain.

1. Gas barrier resin composition layer

As mentioned above, the gas barrier resin composition layer is formed of the gas barrier resin composition. The gas barrier resin composition is composed of a gas barrier resin of an ethylene-vinyl alcohol copolymer (hereinafter, sometimes referred to as "EVOH"), an inorganic layered compound, and additives. In the following, the respective constitutions of the gas barrier resin composition layer are explained.

1-1. Gas barrier resin

EVOH that can be used as a gas barrier resin includes, for example, those obtained by saponifying an ethylene-vinyl acetate copolymer. Specific examples of those obtained by saponifying the ethylene-vinyl acetate copolymer include: those obtained by saponifying an ethylene-vinyl acetate copolymer obtained by copolymerizing ethylene and vinyl acetate; and those obtained by saponifying ethylene and vinyl acetate It is obtained by saponifying an ethylene-vinyl acetate copolymer obtained by copolymerizing with other monomers. In the present invention, the copolymer obtained by copolymerizing ethylene and vinyl acetate, and the copolymer obtained by copolymerizing ethylene and vinyl acetate with other monomers are collectively referred to as "ethylene-vinyl acetate copolymer".

In the case of an ethylene-vinyl acetate copolymer, the ethylene ratio in the monomer composition before copolymerization is preferably 20 mol% to 60 mol%. When the ethylene ratio is 20 mol% or more, the gas barrier properties under high humidity can be further improved, and in addition, the decrease in the strength of the laminate after sterilization can be further suppressed. On the other hand, when the ethylene ratio is 60 mol% or less, the gas barrier properties can be further improved. The ethylene-vinyl acetate copolymer is preferably one whose saponification degree of the vinyl acetate component is 95 mol% or more. If the degree of saponification of the vinyl acetate component is 95 mol% or more, the gas barrier property or oil resistance tends to be better.

In addition, as mentioned above, EVOH can also be treated with peroxides to cut the molecular chain to reduce the molecular weight in order to improve the solubility stability in the solvent.

As mentioned above, "peroxide" includes the following items (1) to (7):

(1)H₂O₂ 。

(2)M₂O₂Type (M: Na, K, NH₄, Rb, Cs, Ag, Li, etc.).

(3)M'O₂Type (M': Mg, Ca, Sr, Ba, Zn, Cs, Hg, etc.).

(4) ROOR type (R represents an alkyl group, and the same hereinafter.): Dialkyl peroxides such as diethyl peroxide.

(5) R-CO-OO-CO-R type: diacetyl peroxide, dipentyl peroxide, dibenzyl peroxide and other acyl peroxides.

(6) Peroxy acid type

a) Acid with -OO- bond: persulfuric acid (H₂SO₅), superphosphoric acid (H₃PO₅)Wait;

b) R-CO-O-OH: performic acid, peracetic acid, perbenzoic acid, perphthalic acid, etc.

(7) Hydrogen peroxide inclusions: (NaOOH)₂/H₂O₂, (KOOH)₂/3H₂O₂Wait.

Among these, hydrogen peroxide is particularly suitable for use because it can be easily decomposed by using a reducing agent, a reducing enzyme, or a catalyst afterwards.

There is no special restriction on the method of treating EVOH with peroxide, and conventional treatment methods can be used. Specifically, for example, a peroxide and a catalyst for cutting molecular chains (for example, iron sulfate, etc.) are added to a solution in which EVOH is dissolved (hereinafter, sometimes referred to as "EVOH solution"), and A method of heating at 40 to 90°C under stirring.

In more detail, taking the peroxide method using hydrogen peroxide as an example, hydrogen peroxide (usually a 35 mass% aqueous solution) is added to the solution obtained by dissolving the EVOH solution in the solvent as described later , And process under stirring at a temperature of 40°C to 90°C for 1 hour to 50 hours. The addition amount of hydrogen peroxide (35 mass% aqueous solution) is about 3 to 300 parts by mass relative to 100 parts by mass of EVOH in the solution. In addition, the catalyst used to cut the molecular chain is to adjust the reaction rate of oxidative decomposition, and a metal catalyst (CuCl) of about 1 ppm to 5000 ppm (mass basis, the same hereinafter) relative to the EVOH solution can be added.₂, CuSO₄, MoO₃, FeSO₄, TiCl₄, SeO₂Wait). The end time of such a process can be regarded as a target when the viscosity of the solution becomes less than about 10% of the initial value. After the treatment is completed, the solvent is removed from the solution by a conventional method, and the terminal carboxylic acid-modified EVOH containing about 0.03 meq/g to 0.2 meq/g carboxyl group at the molecular end can be obtained.

1-2. Inorganic layered compound

As mentioned above, the "inorganic layered compound" is a clay mineral including bentonite, kaolin, mica, hydrotalcite (boehmite), and chlorite. Specifically, its series include: montmorillonite, beidelite, saponite, hectorite, zinc bentonite, talcite, kaolinite, nacre, dickite, halloysite, hydrated halloysite , Tetrasilica mica, sodium taeniolite (sodium taeniolite), muscovite, pearl mica (margarite), phlogopite (bronze mica; phlogopite), talc, chlorophyllite, chrysotile, phyllite, vermiculite, green brittle Mica, chlorite, etc. In addition, scaly silica or the like can also be used. These can be used alone, or two or more of them can be used in combination. Among these, bentonite (including its synthetic products) is particularly preferred.

In addition, metal ions having redox properties in the inorganic layered compound are preferred, and those containing iron ions are particularly preferred. Furthermore, among these, it is preferable to use montmorillonite from the viewpoint of coating suitability and gas barrier properties. Montmorillonite can be used as a conventional gas barrier agent. For example, you can use the general formula: (X, Y)_2~3Z₄O₁₀(OH)₂MH₂O(Wω) [In the formula, X represents Al, Fe(III), Cr(III). Y represents Mg, Fe(II), Mn(II), Ni, Zn, Li. Z stands for Si and Al. W stands for K, Na, and Ca. H₂O represents interlayer water. m and ω are real numbers that represent positive. The montmorillonite group mineral represented. Among these, from the viewpoint of being cleavable in an aqueous medium, W is preferably Na. In addition, the inorganic layered compound has a particle size of 5 μm or less, an aspect ratio of 50 to 5000, and particularly preferably a range of 200 to 3000.

The content of the inorganic layered compound in the gas barrier resin composition (the total of the gas barrier resin, the inorganic layered compound, and the additives is 100% by mass) is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably It is 1.0% by mass or more, more preferably 1.2% by mass or more, and is 9.0% by mass or less, preferably 7.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 5.0% by mass or less. If the content of the inorganic layered compound is less than 0.1% by mass, the gas barrier properties will decrease due to the sterilization treatment, or the laminate strength after the sterilization treatment will decrease. In contrast, if inorganic When the content of the layered compound exceeds 9.0% by mass, the build-up strength and gas barrier properties will decrease due to the sterilization treatment. It can be presumed that the peeling strength between the layers is reduced due to the sterilization treatment, so that peeling occurs between the inorganic film layer and the gas barrier resin layer, or the flexibility of the gas barrier resin layer is reduced. Therefore, due to various stresses during use , Vibration or the stress of the spray water during the sterilization process causes cracks in the gas barrier resin layer and other reasons, resulting in a decrease in gas barrier properties.

At this time, it was generally considered that the blending amount of the inorganic layered compound in the gas barrier resin composition layer is small, the gas barrier properties will be reduced, and if it is large, the gas barrier properties will be increased. Barrier. However, in the case of lamination with an inorganic thin film of the present invention, even if the content of the inorganic stratiform compound in the gas barrier resin composition layer is small, the synergistic effect with the inorganic thin film is caused. Can show high gas barrier properties. It is because the gas barrier resin composition layer on the inorganic thin film layer not only can compensate for the shortcomings of the inorganic thin film due to pinholes or cracks, but also has the function of preventing damage such as breakage of the inorganic thin film, and even the inorganic layered compound A small amount of content can fully fulfill the function of making up for the shortcomings. Conversely, if the content of the inorganic layered compound increases, for example, the indirect focus of the layer during the sterilization process will decrease, and the flexibility of the film will decrease, which will reduce the damage prevention function of the inorganic film. Therefore, on the whole, it is not only The gas barrier property improvement effect cannot be obtained above, but on the contrary, the gas barrier property is reduced.

As mentioned above, the blending amount of the inorganic layered compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass relative to 100 parts by mass of the gas barrier resin as described above. Parts by mass or more, preferably 10 parts by mass or less, more preferably 9 parts by mass or less, and still more preferably 8 parts by mass or less.

1-3. Additives

In the present invention, the gas barrier resin composition may contain at least one of a coupling agent and a crosslinking agent as an additive. The coupling agent is not particularly limited as long as it can be used in the resin composition, but it is preferably a silane coupling agent having at least one or more organic functional groups. The organic functional groups include epoxy groups, amino groups, alkoxy groups, isocyanate groups, and the like.

Specific examples of the aforementioned "silane coupling agent with at least one organic functional group" include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-cyclohexyl) (Oxycyclohexyl) ethyl triethoxy silane, 3-(3,4-epoxycyclohexyl) propyl trimethoxy silane, 2-glycidoxy ethyl trimethoxy silane, 2-glycidoxy group Ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. "Epoxy-containing silane coupling agent"; 2-amino group Ethyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-[N-(2-aminoethyl)amino]ethyl trimethoxysilane Silane, 3-[N-(2-aminoethyl)amino]propyltrimethoxysilane, 3-[N-(2-aminoethyl)amino]propyltriethoxysilane, 3-[N-(2-Aminoethyl)amino]propylmethyldimethoxysilane, etc. "Amino-containing silane coupling agent"; dimethyldimethoxysilane, dimethyldiethyl Oxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc. "alkoxy-containing silane coupling agent"; γ-isocyanate group Propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl dimethoxy silane, γ-isocyanate propyl methyl diethoxy silane, etc. Isocyanate-based silane coupling agent" and so on. These can be used alone, or two or more of them can be used.

As mentioned above, the crosslinking agent is not particularly limited as long as it can be used in the resin composition, but it is preferably a crosslinking agent for a hydrogen-bonding group. Crosslinking agents for hydrogen bonding groups include: water-soluble zirconium compounds, water-soluble titanium compounds, and the like. Specific examples of "water-soluble zirconium compounds" include: zirconium oxychloride, zirconium hydroxychloride, basic zirconium sulfate, zirconium nitrate, ammonium zirconium carbonate, sodium zirconium sulfate, sodium zirconium citrate, zirconium lactate, zirconium acetate, zirconium sulfate , Zirconyl sulfate, zirconyl nitrate, basic zirconium carbonate, zirconium hydroxide, potassium zirconium carbonate, zirconium chloride, zirconium chloride octahydrate, zirconium oxychloride, monohydroxy ginseng (lactic acid) zirconium ammonium, four (lactic acid) ) Ammonium zirconium, monohydroxy ginseng (slate) ammonium zirconium, etc. Among these, from the viewpoints of the suitability for hot water treatment after hot water treatment for improving the coating cohesiveness and the stability of the coating liquid used to form the gas barrier resin composition layer, chlorine oxidation is preferred. Zirconium and zirconium hydroxychloride are particularly preferably zirconium oxychloride. Specific examples of "water-soluble titanium compounds" include: titanium lactate, ammonium titanium lactate, diisopropoxy (triethanolamine) titanium, di-n-butoxy bis(triethanolamine) titanium, diisopropoxy Base bis(triethanolamine) titanium, Si(acetyl ketone acid) titanium, etc. These can be used alone or in combination of two or more kinds.

In the gas barrier resin composition (the total of the gas barrier resin, the inorganic layered compound, and the additives is 100% by mass), the content of the additives (coupling agent and crosslinking agent) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass or more, most preferably 8% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less, most preferably It is 12% by mass or less. By controlling the additive content to be within the above-mentioned range, it is possible to further suppress the decrease in the strength of the laminate after the sterilization treatment.

In addition, the blending amount of the aforementioned additives relative to 100 parts by mass of the aforementioned gas barrier resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass Parts by mass or more, preferably 15 parts by mass or less, more preferably 13 parts by mass or less, and still more preferably 12 parts by mass or less.

1-4. Formation method

The method of forming the gas barrier resin composition layer on the inorganic thin film layer includes: for example, coating the inorganic thin film layer with a coating solution obtained by dissolving and dispersing each material of the gas barrier resin composition in a solvent; The gas barrier resin composition is melt-extruded on the inorganic film layer to be laminated; in addition, the gas barrier resin composition is formed into a film and the adhesive is attached to the inorganic film layer. Among these, from the viewpoints of simplicity, productivity, etc., a method by coating is preferred. In addition, at this time, a tackifying coating layer may be provided on the inorganic thin film layer, and a gas barrier resin composition layer may be provided on the tackifying coating layer. The thickening coating layer will be described later.

Hereinafter, a method of applying a coating solution obtained by dissolving and dispersing each material of the gas barrier resin composition in a solvent on the inorganic thin film layer will be described as an example of the method of forming the gas barrier resin composition layer.

The solvent (solvent) used to make the gas barrier resin composition into the coating liquid can use either aqueous or non-aqueous solvents that can dissolve EVOH, but it is preferable to use a mixed solvent of water and lower alcohol. Specifically, it is preferably water and a lower alcohol with a carbon number of 2 to 4 (ethyl alcohol, n-propanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary Butyl alcohol, etc.) mixed solvents. If these mixed solvents are used, the solubility of EVOH will tend to be good while maintaining a moderate solid content. The content of the lower alcohol in the mixed solvent is preferably 15% by mass to 70% by mass. If the lower alcohol content in the mixed solvent is 70% by mass or less, when the inorganic layered compound is dispersed as described above, the cleavage of the inorganic layered compound can be further carried out. In addition, if it is 15% by mass or more In this case, the coating suitability of the coating liquid obtained by dissolving and dispersing the gas barrier resin composition can be further improved.

The method of dissolving and dispersing the gas barrier resin composition in a solvent is not particularly limited. It includes, for example, adding and mixing an inorganic layered compound in the EVOH solution (if necessary, it can also be pre-swollen, pyrolyzed and dispersed in water. Medium), and the method of dispersing the inorganic layered compound; adding (dissolving) EVOH to the dispersion of the swelling and pyrolysis of the inorganic layered compound in a dispersion medium such as water (you can also pre-dissolve it in a solvent if necessary) The method and so on. At this time, the mass ratio of the gas barrier resin composed of EVOH to the inorganic layered compound is such that the content of the inorganic layered compound relative to 100 parts by mass of the gas barrier resin composition is 0.1 to 10 parts by mass The amount of the range of parts to be mixed.

When performing such mixing, the inorganic layered compound can be uniformly dispersed by a conventional stirring device or dispersion device, but in order to obtain a particularly transparent and stable inorganic layered compound dispersion, a high-pressure disperser can be used. The high-pressure dispersing machine includes, for example, Gaulin homogenizer (manufactured by APV Gaulin), nano-homogenizer (NANOMIZER) (manufactured by Nanomizer), high-pressure nano-homogenizer (MICOFLUIDIZER) (manufactured by Microfluidics Corporation (Microfluidics Corporation)), ULTIMIZER (Manufactured by Sugino Machine Limited), DeBee (manufactured by Bee), etc. The pressure condition of these high-pressure dispersers is preferably 100 MPa or less for dispersing treatment. If the pressure condition is 100 MPa or less, the pulverization of the inorganic layered compound can be suppressed, and the intended gas barrier properties can be improved. In addition, since the mixing of additives can be carried out only by stirring, it can be added at any time. However, from the viewpoint of suppressing the influence of additives as much as possible, it is preferable that the inorganic layered compound has been dispersed in the EVOH solution. Add additives at the end of the stage. The coating method can be used according to the characteristics of the coating liquid: gravure rotary coating, bar coating, die coating, spray coating and other previous methods.

1-5. Drying conditions of coating liquid for gas barrier resin composition layer

The drying temperature after applying the coating liquid of the gas barrier resin composition is preferably 100°C or higher, more preferably 130°C or higher, still more preferably 150°C or higher, and 200°C or lower. In addition, the additional heat treatment in another processing step, that is, once the film is wound, it is unrolled, or rolled with a roll, or an additional heat treatment is performed before or in the middle of subsequent steps such as the lamination step ( 150 to 200°C) measures are also effective. If the drying temperature is above 100°C, the coating layer can be sufficiently dried to crystallize or crosslink the gas barrier resin composition layer, so that the gas barrier properties and laminate strength after the sterilization treatment tend to be better. . On the other hand, if the drying temperature is less than 200°C, the application of excessive heat to the plastic film can be suppressed to prevent the film from becoming fragile or causing shrinkage, and the processability tends to be good.

1-6. The thickness of the gas barrier resin composition layer

The thickness of the gas barrier resin composition layer is 0.05 μm or more, preferably 0.10 μm or more, more preferably 0.15 μm or more, and 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.2 μm or less. If the thickness is thinner than 0.05μm, the gas barrier after sterilization will be reduced. On the contrary, if the thickness is more than 0.5μm, when the coating solution is used, the gas barrier will be reduced. As a result of insufficient drying of the coating solution, the gas barrier resin composition layer becomes fragile, resulting in a decrease in the strength of the laminate after the sterilization treatment.

2. Plastic film

The plastic film used in the present invention is a film made of organic polymer resin, and after being melted and extruded, it is stretched, cooled, and thermally fixed in the length direction and/or width direction as needed. As mentioned above, "organic polymer" includes: polyamide, polyester, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamidoimide, Polyimide, polyimide, polyimide, polystyrene, polylactic acid, etc.

As mentioned above, specific examples of "polyamide" include: polyhexanamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), Polyundecylamide (nylon 11), polylaurinlactam (nylon 12), polyethylene diamine hexadiamide (nylon 2,6), polytetrafluoroethylene Methyl hexamethylene diamide (nylon 4,6), polyhexamethylene hexamethylene diamide (nylon 6,6), polyhexamethylene sebacamide (nylon 6,10), polyhexamethylene Dodecamide (nylon 6,12), polyoctamethylene hexamethylene amide (nylon 6,12), polyoctamethylene hexamethylene amide (nylon 8,6), polydecamethylene hexamethylene Amide (nylon 10,6), polydecamethylene sebacamide (nylon 10,10), polydodecamethylene dodecamide (nylon 12,12), stubble diamine-6 Nylon (MXD6) and so on. In addition, it can also be a copolymer with this as the main component. Examples include: caprolactam/azatridecane-2-one copolymer, caprolactam/hexamethylene adipate Diammonium copolymer, azacyclotridecane-2-one/hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer, Ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, caprolactam/hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer, etc. Among these polyamides, flexible modifying ingredients that can be blended into films include: aromatic sulfonamides, p-hydroxybenzoic acid, esters, etc. plasticizers or low elastic modulus elastomer components Or internal amines are also effective.

Specific examples of "polyester" as mentioned above include: polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate and the like. In addition, it can also be a copolymer with this as the main component, and if a polyester copolymer is used, its dicarboxylic acid component can be used: terephthalic acid, isophthalic acid, phthalic acid or 2, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid; multifunctional carboxylic acids such as trimellitic acid and pyromellitic acid; aliphatic dicarboxylic acids such as adipic acid and secretory acid. In addition, glycol components can be used: aliphatic diols such as ethylene glycol, 1,4-butanediol, diethylene glycol, propylene glycol, and neopentyl glycol; aromatic diols such as paraben diols ; 1,4-cyclohexanedimethanol and other alicyclic diols; polyethylene glycol with an average molecular weight of 150 to 20,000. In 100 mol% polyester, the preferred copolymerization component ratio is 20 mol% or less. If the copolymer component is more than 20 mol%, the film strength, transparency, heat resistance, etc. may deteriorate. These organic polymers can also be further copolymerized with a small amount of other monomers or blended with other organic polymers.

In addition, when the gas barrier laminate film of the present invention is used as a barrier film for solar cells, a barrier film for organic electroluminescence, or a barrier film for electronic paper, the organic polymer resin used to form the plastic film is preferably Polyethylene terephthalate or polyethylene naphthalate. Especially when used as a barrier film for solar cells, since high hydrolysis resistance is required, the acid value of the plastic film is preferably 10 equivalents/ton or less, more preferably 5 equivalents/ton or less.

In addition, when polyethylene terephthalate is used, its inherent viscosity (IV value) is preferably 0.60 or more, more preferably 0.65 or more, and preferably 0.90 or less, more preferably 0.80 or less. In addition, the IV value is a value measured at 30°C in a mixed solvent of phenol/1,1,2,2-tetrachloroethane (6/4 mass ratio). In addition, the content of the cyclic trimer in the polyethylene terephthalate is preferably 0.7% by mass or less, more preferably 0.5% by mass or less.

In addition, the polycondensation catalyst of polyethylene terephthalate or polyethylene naphthalate is a compound including antimony, germanium, titanium, aluminum, phosphorus, etc., among which aluminum compounds and phosphorus are preferred. For the polymerization catalyst composed of the compound, the catalyst disclosed in Japanese Patent Laid-Open No. 2002-249565 can be used. As mentioned above, the "aluminum compound" is preferably aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum acetylacetonate, and the like. As mentioned above, the phosphorus compound is preferably a phosphonic acid compound having a hindered phenol structure, and specific examples include Irganox (registered trademark) 1222, 1425 (manufactured by Ciba Seika Co., Ltd.).

In addition, conventional additives such as ultraviolet absorbers, antistatic agents, plasticizers, lubricants, colorants, etc. can also be added to the organic polymer resins described above. As described above, the thickness of the plastic film is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more, and preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less. As mentioned above, the transparency of the plastic film is not particularly limited, but when it is used as a transparent packaging material laminate, it is preferably one with a light transmittance of 50% or more. On the other hand, as mentioned above, the plastic film may also be a laminated film. There are no particular restrictions on the type of laminate, the number of laminates, the method of laminate, etc. when it is intended to be a laminate film, and it can be arbitrarily selected from conventional methods according to the purpose.

As for the manufacturing method of the plastic film, existing methods such as extrusion method and casting method can be used. In the plastic film of the present invention, as long as it is within the scope that does not impair the purpose of the present invention, corona discharge treatment, glow discharge, flame treatment, and surface roughening treatment can be applied to the plastic film in advance before lamination of the inorganic film layer. In addition, conventional tackifying coating treatment, printing, and decoration can also be applied.

3. Inorganic thin film layer

As mentioned above, the inorganic thin film layer is a thin film composed of metal or inorganic oxide. The material used to form the metal thin film is not particularly limited as long as it can be made into a thin film. It includes, for example, magnesium, aluminum, titanium, chromium, nickel, indium, etc., but from the viewpoint of cost, etc. , It is preferably aluminum. In addition, the material used to form the inorganic oxide thin film is not particularly limited as long as it can be made into a thin film. It includes, for example, silicon oxide, aluminum oxide, magnesium oxide, etc., and preferably silicon oxide, Aluminum oxide, magnesium oxide. Among these, due to its superior gas barrier properties, a multi-element inorganic oxide film containing silica and alumina is more preferred, and a silica-alumina binary inorganic oxide film is most preferred. Here, the so-called "silicon oxide" means SiO or SiO₂A mixture of various silicon oxides, and the so-called "alumina" means AlO or Al₂O₃A mixture of various aluminum oxides.

In addition, the reason why the multi-element inorganic oxide film containing silicon oxide and alumina has superior gas barrier properties is that the multi-element inorganic oxide film can change the flexibility and gas barrier of the film by the ratio of inorganic substances in the film. Performance to produce a good film with balanced properties. In addition, if an adhesive layer is provided on the inorganic thin film layer as will be described later, it is easy to obtain high adhesion between the multi-element inorganic oxide thin film containing silicon oxide and aluminum oxide and the adhesive layer.

When it is to be formed into a silica-alumina binary inorganic oxide film, the content of alumina in the inorganic oxide film is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably It is 40% by mass or more, preferably 99% by mass or less, more preferably 75% by mass or less, and still more preferably 60% by mass or less. If the content of alumina in the silica-alumina binary inorganic oxide film is 20% by mass or more, the gas barrier properties can be further improved, and if it is 99% by mass or less, it can make evaporation The flexibility of the coating tends to be good, which makes the gas barrier laminated film stronger against bending or dimensional changes, and further improves the efficacy of both.

In addition, if D=0.01A+b (D: the specific gravity of the film, A: the mass% of alumina in the film) represents the ratio of the specific gravity of the inorganic oxide film and the content of alumina in the inorganic oxide film (mass%) If the value of b is in the area less than 1.6, the structure of the silica-alumina-based thin film will become thicker. In addition, if the value of b is in the area greater than 2.2, the silica-alumina binary system inorganic The oxide film has a tendency to harden.

Therefore, as the inorganic oxide film, the specific gravity of the silica-alumina binary inorganic oxide film is based on the specific gravity of the film and the content of alumina in the film (mass%) D=0.01A+b( When represented by the relational expression of D: specific gravity of the film, A: content of alumina in the film), the b value is preferably 1.6 to 2.2, and more preferably 1.7 to 2.1, but it is not limited to this range. The multi-element inorganic oxide film containing silicon oxide and aluminum oxide and further containing other inorganic oxides is also effective as a gas barrier laminate.

In the present invention, the thickness of the inorganic thin film layer is preferably 1 nm or more, more preferably 5 nm or more, and preferably 800 nm or less, more preferably 500 nm or less. If the film thickness is 1 nm or more, the gas barrier properties can be further improved. In addition, even if it exceeds 800 nm and is made too thick, the gas barrier property improvement effect equivalent to it cannot be obtained.

Take the silica-alumina binary inorganic oxide film as an example to illustrate the method of forming the inorganic film layer as follows. The thin film formation method by the vapor deposition method can be appropriately selected and used: a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a CVD method (chemical vapor deposition method), etc. For example, in the case of a vacuum evaporation method, the evaporation material is SiO₂With Al₂O₃Mixture, or SiO₂Mixtures with Al, etc. Heating can use resistance heating, high-frequency induction heating, electron beam heating, etc. In addition, oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor can be introduced as reaction gases, etc., and ozone addition and ion acceleration can also be used. And other methods of reactive evaporation. In addition, film forming conditions such as applying a bias voltage to the plastic film, heating the plastic film, or cooling the plastic film can also be arbitrarily changed. The vapor deposition material, reaction gas, substrate bias, heating and cooling, etc., as described above, can also be changed in the same way when sputtering or CVD is used. By the above method, it is possible to achieve transparency and superior gas barrier properties, to withstand various treatments, such as boiling treatment or sterilization treatment, and furthermore to withstand the Gelbo Flexibility Test (Gelbo Flex Durability test) (bending resistance test) superior performance gas barrier laminated film.

4. Tackifying coating layer

The gas barrier multilayer film of the present invention preferably has an adhesion-promoting coating layer between the inorganic thin film layer and the gas barrier resin composition layer. Due to the adhesion-promoting coating layer, the adhesion between the inorganic thin film layer and the gas barrier resin composition layer can be further improved.

As mentioned above, the thickening coating layer is formed of a composition for thickening coating layer containing a resin composition of a thickening coating agent and a solvent. The "tackifying coating agent resin composition" includes, for example, urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, polybutadiene-based resins, etc. Add hardeners such as epoxy, isocyanate, melamine, etc. The winner. As mentioned above, the "solvent (solvent)" includes, for example, aromatic solvents such as benzene and toluene; alcoholic solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate , Ester solvents such as butyl acetate; Polyol derivatives such as ethylene glycol monomethyl ether, etc.

In addition, the resin composition of the thickening coating agent preferably contains a silane coupling agent having at least one organic functional group. The organic functional group includes: alkoxy group, amino group, epoxy group, isocyanate group and the like. In the resin composition of the thickening coating agent (the total of the resin, the curing agent, and the silane coupling agent is 100% by mass), the addition amount of the silane coupling agent is preferably 0.1% by mass or more, more preferably 3% by mass or more, and Preferably it is 10 mass% or less, More preferably, it is 7 mass% or less. If the added amount is 0.1% by mass or more, the strength of the laminate after sterilization can be further improved.

The thickness of the adhesion-promoting coating layer is preferably 0.05 μm or more, more preferably 0.10 μm or more, still more preferably 0.15 μm or more, and preferably 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.25 μm or less . If the thickness of the thickening coating layer is 0.05 μm or more, the decrease in the strength of the build-up layer caused by the sterilization treatment can be further suppressed, and if it is 0.5 μm or less, the gas barrier properties can be more inclined without the occurrence of coating spots. Yu good.

5. Base coating

In the gas barrier multilayer film of the present invention, a primer coat layer may also be provided between the plastic film and the inorganic film layer. By providing the base coating, the flatness of the gas barrier laminated film can be improved, or the adhesion between the plastic film and the inorganic film layer can be further improved.

The base coat layer can be formed by a coating liquid for base coat layer in which the resin component for constituting the base coat layer is dissolved or dispersed. The resin used to form the base coating layer includes, for example, polyurethane resin and copolymerized polyester resin. In particular, the resin used to form the base coat layer is preferably a combination of a polyurethane resin and a copolymerized polyester resin.

6. Laminated with other films, etc.

The gas barrier laminated film of the present invention can be used for food packaging applications and various applications, and can be further combined with heat seal layers, printing layers, other resin films, adhesive layers for bonding these layers, etc. The other materials are layered. In the lamination, conventional methods such as the method of directly melt-extrusion on the gas barrier laminated film of the present invention to laminate, the method of coating, the method of laminating the films directly or through an adhesive, etc. . In addition, when high barrier properties are required, two or more gas barrier laminate films of the present invention may be laminated.

For example, when used as a cover material for a retort pouch or the like or a retort food, it is preferable to provide a heat seal layer of polyethylene or polypropylene on the gas barrier resin composition layer . In addition, other resin films may be laminated between the gas barrier resin composition layer and the heat seal layer. As other resin films, the resin films listed as plastic films can be used. When performing such lamination, the lamination can be carried out through the adhesive agent.

In addition, when used as a solar cell, a weather resistant film such as a fluorine-based film or a hydrolysis-resistant polyester film, a light reflective white film, a black colored film, etc. can be laminated on the gas barrier laminated film of the present invention. It is used as a backplane. When used as a film on the light-receiving side of a solar cell, an anti-fouling coating, a reflection reduction coating, an anti-glare coating, a hard coating, etc. can be provided on the gas barrier laminated film of the present invention, and it can also be laminated Other films to which these coatings have been applied. In addition, in the case of organic EL or electronic paper applications, antifouling coatings, reflection reduction coatings, anti-glare coatings, hard coatings, etc. can also be provided, and other films coated with these coatings can also be laminated. These other coatings and other films can be provided on any side of the gas barrier laminated film of the present invention.

"Examples"

Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited to those described below. Various changes can be made without departing from the scope of the context. However, these should be included in Within the technical scope of the present invention.

1. Evaluation method

1-1. Manufacturing of multilayer gas barrier multilayer film

On top of the gas barrier resin composition layer of the gas barrier laminated film No. 1 to 23 (No. 16 is on the adhesion-promoting coating layer), a dry laminated layer using a urethane-based two-component curing adhesive Method, laminating non-stretched polypropylene film ("P1147" (thickness 70μm), manufactured by Toyobo Co., Ltd.) as a heat-adhesive resin, and aging at 40°C for 4 days to obtain a laminated gas barrier laminated film . In addition, the thickness of the adhesive layer after drying was 3 μm.

1-2. Measurement of water vapor transmission

The laminated gas barrier laminated film is based on the JIS K7129 B method, using a water vapor transmission measuring device ("PERMATRAN-W 3/33MG", manufactured by MOCON), in an atmosphere with a temperature of 40°C and a humidity of 100% RH Determine the water vapor transmission rate. In addition, for the humidity control of the gas barrier laminated film, the direction in which water vapor permeates from the plastic film side to the gas barrier resin composition layer side is adopted. In addition, the gas barrier laminated film has a temperature of 121°C and a pressure of 0.2MPa (2kgf/cm).²After applying a sterilization treatment for 30 minutes under ), the water vapor permeability was measured in the same manner for the obtained obtained by drying at 40°C for 1 day.

1-3. Oxygen permeability

The laminated gas barrier laminated film is based on the criteria of JIS K7126-1 (2006) Annex 1, using an oxygen permeability measuring device ("OX-TRAN 2/20", manufactured by MOCON) at a temperature of 23°C and a humidity of 65% The oxygen permeability is measured under the atmosphere of RH. In addition, the gas barrier laminated film has a temperature of 121°C and a pressure of 0.2MPa (2kgf/cm).²After applying a sterilization treatment for 30 minutes under) and drying at 40°C for 1 day, the oxygen permeability was also measured in the same manner.

1-4. Measuring method of build-up strength

Cut the laminated gas barrier laminated film into a test piece with a width of 15mm and a length of 200mm, and use a TENSILON universal material testing machine ("TENSILON UMT-II-500") at a temperature of 23°C and a relative humidity of 65%. Type'', manufactured by Orientec Co., Ltd.) to measure the build-up strength . In addition, the stretching speed was 200 mm/min, and water was wetted between the gas barrier laminate film and the unstretched polypropylene film, and the strength when peeled at a peeling angle of 90 degrees was measured. In addition, the gas barrier laminated film has a temperature of 121°C and a pressure of 0.2MPa (2kgf/cm).²After applying a sterilization treatment for 30 minutes under ), the obtained product was dried at 40°C for 1 day, and the laminate strength was measured in the same manner.

1-5. The thickness of the gas barrier resin composition layer

Cut the sample of the gas barrier laminated film into a long poem of 2mm×5mm, and embed it in epoxy resin. The embedded sample was cut into ultra-thin sections with a microtome, and stained with an osmium tetroxide stain. The observation was performed using a transmission electron microscope (manufactured by JEOL Ltd., "JEM2100"), and the acceleration voltage was 200 kV, and the observation magnification was 5,000 times and 10,000 times to observe to measure the thickness of the gas barrier resin composition layer.

2. Preparation

2-1. Manufacturing of plastic film

Pre-crystallized polyethylene terephthalate (PET) with an ultimate viscosity of 0.62 (measured at 30°C, phenol/tetrachloroethane (mass ratio) = 60/40) and 100ppm silica After that, it was dried by a conventional method, and then extruded at 280°C using an extruder equipped with a T-die, and quenched and solidified on a drum with a surface temperature of 40°C to obtain an amorphous flake. Next, the obtained sheet was stretched 4 times in the longitudinal direction at 100° C. between the heating roller and the cooling roller to obtain a uniaxially stretched PET film.

2-2. Preparation of coating liquid used to form the thickening coating layer

&lt;Preparation example 1&gt;

Add an isocyanate-based hardener ("TAKELAC A-50", manufactured by Mitsui Chemicals Co., Ltd.) to a urethane-based resin ("TAKELAC (registered trademark) A525-S", manufactured by Mitsui Chemicals Co., Ltd.), And the solvent is prepared by using ethyl acetate to have a solid content concentration of 6.5% by mass. For this, epoxy-based silane coupling agent ("KBM403", manufactured by Shin-Etsu Chemical Co., Ltd.) is added to the resin composition of the thickening coating agent (the total of resin, hardener, and silane coupling agent is 100% by mass) The content in is 5% by mass, which is used as coating liquid No. 1 for the thickened coating layer.

&lt;Preparation example 2&gt;

Except that the silane coupling agent was changed to an isocyanate-based silane coupling agent ("KBE9007", manufactured by Shin-Etsu Chemical Co., Ltd.), the viscosity-increasing coating layer solution coating solution No. 2 was prepared in the same manner as in Preparation Example 1.

&lt;Preparation example 3&gt;

Except that the silane coupling agent was changed to an amine silane coupling agent ("KBM603", manufactured by Shin-Etsu Chemical Co., Ltd.), the viscosity-increasing coating layer solution coating solution No. 3 was prepared in the same manner as in Preparation Example 1.

&lt;Preparation example 4&gt;

In addition to changing the resin to a urethane resin ("EL-530A", manufactured by Toyo-Morton), and changing the hardener to an isocyanate-based hardener ("EL-530B", manufactured by Toyo-Morton) 4. Except for the rest, the coating solution No. 4 for the thickening coating layer was prepared in the same manner as in Preparation Example 1.

&lt;Preparation example 5&gt;

To urethane-based resin ("TAKELAC (registered trademark) A525-S", manufactured by Mitsui Chemicals Co., Ltd.), an isocyanate-based hardener ("TAKELAC A-50", manufactured by Mitsui Chemicals Co., Ltd.) is added 5. And the solvent is prepared using ethyl acetate to have a solid content concentration of 6.5% by mass, and this is used as the coating liquid No. 5 for the thickening coating layer.

2-3. Preparation of gas barrier resin composition layer material

&lt;Preparation of ethylene-vinyl alcohol copolymer solution&gt;

In a mixed solvent of 20.996 parts by mass of purified water and 51 parts by mass of n-propanol (NPA), 15 parts by mass of ethylene-vinyl alcohol copolymer [trade name: "SG-525" (ethylene-vinyl acetate copolymer is saponified) The obtained polymer, the ethylene ratio is 26 mol%, the saponification degree of the vinyl acetate component is about 100%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (hereinafter, sometimes referred to as "EVOH".)], In addition, 13 parts by mass of hydrogen peroxide solution (with a concentration of 30% by mass) and 0.004 parts by mass of iron sulfate (FeSO₄) And heated to 80°C under stirring for reaction for about 2 hours. After that, it is cooled, catalase is added to 3000 ppm, and residual hydrogen peroxide is removed, thereby obtaining a substantially transparent ethylene-vinyl alcohol copolymer with a solid content of 15% by mass. Substance solution (EVOH solution).

&lt;Preparation of polyvinyl alcohol resin solution&gt;

To 70 parts by mass of a mixed solvent composed of 40% by mass purified water and 60% by mass n-propanol (NPA), 30 parts by mass of fully saponified polyvinyl alcohol resin (trade name: "GOHSENOL (registered trademark)" NL-05" (with a saponification degree of 99.5% or more), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and dissolve it to obtain a transparent polyvinyl alcohol solution with a solid content of 30% by mass.

&lt;Preparation of inorganic layered compound dispersion&gt;

4 parts by mass of montmorillonite (trade name: "Kunipia (registered trademark) F", manufactured by Kunimine Industrial Co., Ltd.), which is an inorganic layered compound, was added to 96 parts by mass of purified water while stirring, and a high-pressure dispersion device was used The pressure is set at 50 MPa to fully disperse it. Thereafter, it was kept at 40° C. for 1 day to obtain an inorganic layered compound dispersion with a solid content of 4% by mass.

&lt;Additives&gt;

Crosslinking agent: zirconium oxychloride (trade name "Zircosol (registered trademark) Zc-20" (solid content 20% by mass), manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.).

Crosslinking agent: titanium lactate (trade name: "Orgatics (registered trademark) TC-310" (solid content approximately 45% by mass), manufactured by Matsumoto Pharmaceutical Co., Ltd.).

Silane coupling agent: 3-glycidoxypropyltriethoxysilane (trade name: "KBE-403" (solid content 100% by mass), manufactured by Shin-Etsu Chemical Co., Ltd.).

2-4. Preparation of coating solution for forming gas barrier resin composition layer

&lt;Preparation example 1&gt;

31.75 parts by mass of EVOH solution was added to 62.30 parts by mass of mixed solvent A (refined water: n-propanol (mass ratio)=40:60), and fully stirred and mixed. Furthermore, 5.95 parts by mass of the inorganic layered compound dispersion liquid was added while stirring this solution at a high speed. Add 3 parts by mass of cation exchange resin to 100 parts by mass of the dispersion, and stir for 1 hour at a stirring speed that does not break the ion exchange resin to remove cations, and then use strainer to exchange only cations. The resin is separated by filtration.

The dispersion liquid obtained by the above operation is further subjected to dispersion treatment in a high-pressure dispersion device with a pressure of 50 MPa. Add 0.75 parts by mass of zirconium oxychloride, 0.9 parts by mass of purified water, and 1.35 parts by mass of NPA as additives to 97 parts by mass of the mixed solution after dispersion treatment. The filter screen is filtered to obtain a coating liquid No. 1 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 2&gt;

Except that the usage amount of mixed solvent A, EVOH solution and inorganic layered compound dispersion was changed to 65.76 parts by mass of mixed solvent A, 33.00 parts by weight of EVOH solution, and 1.24 parts by weight of inorganic layered compound dispersion, the rest was the same as the preparation example 1 In the same manner, to obtain a coating liquid No. 2 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 3&gt;

Except that the usage amount of mixed solvent A, EVOH solution, and inorganic layered compound dispersion was changed to 64.00 parts by mass of mixed solvent A, 32.36 parts by mass of EVOH solution, and 3.64 parts by mass of inorganic layered compound dispersion, the rest are the same as the preparation example 1 In the same manner, to obtain a coating liquid No. 3 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 4&gt;

Except that the usage amount of mixed solvent A, EVOH solution and inorganic layered compound dispersion was changed to 66.21 parts by mass of mixed solvent A, 33.17 parts by mass of EVOH solution, and 0.62 parts by mass of inorganic layered compound dispersion, the rest is the same as the preparation example 1 In the same manner, to obtain a coating liquid No. 4 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 5&gt;

Except that the usage amount of mixed solvent A, EVOH solution and inorganic layered compound dispersion was changed to 60.67 parts by mass of mixed solvent A, 31.15 parts by weight of EVOH solution, and 8.18 parts by weight of inorganic layered compound dispersion, the rest was the same as the preparation example 5. 1 In the same manner, to obtain a gas barrier resin composition layer forming coating liquid No. 5 with a solid content of 5% by mass.

&lt;Preparation example 6&gt;

Except that the additives were changed to 0.15 parts by mass of 3-glycidoxypropyltriethoxysilane, the usage amount of purified water and NPA was changed to 1.14 parts by mass of purified water, and 1.71 parts by mass of NPA, the rest were prepared with 6. In the same manner as in Example 1, to obtain a gas barrier resin composition layer forming coating liquid No. 6 with a solid content of 5% by mass.

&lt;Preparation example 7&gt;

Except that the additives were changed to 0.33 parts by mass of titanium lactate, purified water and the amount of NPA used to 1.07 parts by mass of purified water and 1.60 parts by mass of NPA, the rest was done in the same manner as in Preparation Example 1 to obtain a solid content of 7. 5 mass% of gas barrier resin composition layer formation coating liquid No. 7.

&lt;Preparation example 8&gt;

Except that the usage amount of mixed solvent A, EVOH solution and inorganic layered compound dispersion was changed to 59.10 parts by mass of mixed solvent A, 30.58 parts by weight of EVOH solution, and 10.32 parts by weight of inorganic layered compound dispersion, the rest is the same as the preparation example 8. 1 In the same manner, to obtain a gas barrier resin composition layer forming coating liquid No. 8 with a solid content of 5% by mass.

&lt;Preparation example 9&gt;

To 61.52 parts by mass of the mixed solvent A, 32.40 parts by mass of the EVOH solution was added and fully stirred and mixed. Furthermore, 6.08 parts by mass of the inorganic layered compound dispersion liquid was added while stirring this solution at a high speed. Add 3 parts by mass of cation exchange resin to 100 parts by mass of the dispersion, and stir for 1 hour at a stirring speed that does not break the ion exchange resin to remove cations, and then filter only the cation exchange resin with a strainer Separate.

The dispersion liquid obtained by the above operation is further subjected to dispersion treatment in a high-pressure dispersion device at a pressure of 50 MPa, and 97 parts by mass of the dispersion-treated mixed liquid is added with 0.25 parts by mass of zirconium oxychloride, and 2.75 parts by mass of solvent A was mixed and mixed and stirred, and then filtered with a 255 mesh filter to obtain coating liquid No. 9 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 10&gt;

29.46 parts by mass of EVOH solution was added to 65.02 parts by mass of mixed solvent A, and stirred and mixed thoroughly. Furthermore, 5.52 parts by mass of the inorganic layered compound dispersion liquid was added while stirring this solution at a high speed. Add 3 parts by mass of cation exchange resin to 100 parts by mass of the dispersion, and stir for 1 hour at a stirring speed that does not break the ion exchange resin to remove cations, and then filter only the cation exchange resin with a strainer Separate.

The dispersion obtained by the above operation is further subjected to dispersion treatment in a high-pressure dispersion device with a pressure of 50 MPa, and then 2.50 parts by mass of zirconium oxychloride is added to 97 parts by mass of the mixed solution after dispersion treatment, and 0.50 parts by mass of solvent A was mixed and mixed and stirred, and then filtered with a 255 mesh filter to obtain coating liquid No. 10 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation Example 11&gt; (Excluding inorganic layered compound)

33.33 parts by mass of EVOH solution was added to 66.67 parts by mass of mixed solvent A, and stirred and mixed thoroughly. Furthermore, 3 parts by mass of cation exchange resin was added to this 100 parts by mass of solution, and stirred for 1 hour at a stirring speed that would not cause the ion exchange resin to break to remove cations, and then only the cation exchange resin was added to the coarse filter. Separated by filtration.

To 97 parts by mass of the mixture obtained as described above, 0.75 parts by mass of zirconium oxychloride and 2.25 parts by mass of mixed solvent A were added and mixed and stirred, and then filtered with a 255 mesh filter to obtain a solid 11. Coating liquid No. 11 for forming a gas barrier resin composition layer with a component content of 5% by mass.

&lt;Preparation example 12&gt; (Using polyvinyl alcohol resin)

15.87 parts by mass of the polyvinyl alcohol resin solution were added to 78.17 parts by mass of mixed solvent A, and the mixture was sufficiently stirred and mixed. Furthermore, 5.95 parts by mass of the inorganic layered compound dispersion liquid was added while stirring this solution at a high speed. Add 3 parts by mass of cation exchange resin to 100 parts by mass of the dispersion, and stir for 1 hour at a stirring speed that does not break the ion exchange resin to remove cations, and then filter only the cation exchange resin with a strainer Separate.

The dispersion liquid obtained by the above operation is further subjected to dispersion treatment in a high-pressure dispersion device at a pressure of 50 MPa, and then 0.75 parts by mass of zirconium oxychloride and 0.75 parts by mass of zirconium oxychloride and 2.25 parts by mass of solvent A are mixed and mixed and stirred, and then filtered with a 255 mesh filter to obtain coating liquid No. 12 for forming a gas barrier resin composition layer with a solid content of 5% by mass.

&lt;Preparation example 13&gt; (without additives)

31.75 parts by mass of EVOH solution was added to 62.30 parts by mass of mixed solvent A, and fully stirred and mixed. Furthermore, 5.95 parts by mass of the inorganic layered compound dispersion liquid was added while stirring this solution at a high speed. Add 3 parts by mass of cation exchange resin to 100 parts by mass of the dispersion, and stir for 1 hour at a stirring speed that does not break the ion exchange resin to remove cations, and then filter only the cation exchange resin with a strainer Separate.

The dispersion obtained by the above operation is further dispersed in a high-pressure dispersion device at a pressure of 50 MPa, and then filtered with a 255 mesh filter to obtain a solid content of 5 13. Mass% of coating liquid No. 13 for forming a gas barrier resin composition layer.

3. Manufacturing of gas barrier laminated film

&lt;Manufacturing example 1&gt;

The uniaxially stretched PET film obtained as described above was stretched 4.0 times in the lateral direction at a temperature of 120°C, and subjected to a 6% relaxation treatment in the lateral direction, while setting the temperature of the heat-fixing area to 225°C. Heat fixation treatment. The treatment time at each temperature is 100°C of the preheating temperature for 3 seconds, the stretching temperature of 120°C for 5 seconds, and the heat-fixing treatment temperature of 225°C for 8 seconds. After that, it was cooled, cut to remove both edges, and a biaxially stretched PET film with a thickness of 12 μm and a length of 1000 m or more was continuously manufactured to obtain a roll film. The obtained roll film was slit into a width of 400 mm and a length of 1000 m, and wound on a 3-inch paper tube to obtain a PET film. Then, a binary inorganic oxide thin film layer of silicon oxide and aluminum oxide (ratio of silicon oxide/alumina (mass ratio)=60/40) was formed on the PET film as an inorganic thin film layer.

At this time, the inorganic thin film layer uses granular SiO with a size of about 3 mm to 5 mm₂(Purity is 99.99%) and Al₂O₃(Purity is 99.9%) is used as the evaporation source, and the binary inorganic oxide film of alumina and silicon dioxide is formed by the electron beam evaporation method. The vapor deposition material is not mixed but divided into two parts. The heating source uses an EB (Electron Beam) gun and heats Al in a time-sharing manner.₂O₃With SiO₂. And, set the radiation current of the EB gun at that time to 1.2 A, and make Al₂O₃With SiO₂The mass ratio becomes 40:60 to heat each material. And, set the film conveying speed to 30 m/min, and adjust the pressure during vapor deposition to 1×10^-2Pa. In addition, the temperature of the roller used to cool the film during vapor deposition was adjusted to -10°C. The thickness of the inorganic thin film layer obtained as described above is 27 nm.

On the inorganic thin film layer, coating liquid No. 1 for the adhesion-promoting coating layer was coated by the gravure rotary roll coating method and dried to form the adhesion-promoting coating layer. The thickness of the adhesion-promoting coating layer after drying is 0.30μm. On the adhesion-promoting coating layer, coating liquid No. 1 for forming a gas barrier resin composition layer was applied by a gravure rotary roll coating method, and dried at 160°C to form a gas barrier resin composition layer to produce gas Barrier laminated film No. 1. In addition, the thickness of the gas barrier resin composition layer after drying was 0.25 μm.

&lt;Manufacturing Examples 2 to 10&gt;

Except that the coating liquid for forming the gas barrier resin composition layer was changed to the coating liquid for forming the gas barrier resin composition layer No. 2 to 10, the gas barrier laminated film No. was produced in the same manner as in Production Example 1. . 2 to 10.

&lt;Manufacturing Example 11&gt;

Except that the mass ratio of silicon oxide to aluminum oxide (silica/alumina) in the inorganic thin film layer of the binary system oxide of silicon oxide and aluminum oxide is changed to 50/50, the rest is performed in the same manner as in Manufacturing Example 1. Manufactured gas barrier multilayer film No. 11.

&lt;Manufacturing Examples 12 to 15&gt;

Except that the coating liquid for the thickening coating layer was changed to coating liquid Nos. 2 to 5 for the thickening coating layer, the gas barrier laminated film Nos. 12 to 15 were produced in the same manner as in Production Example 1.

&lt;Manufacturing Example 16&gt;

Except that the gas barrier resin composition layer was not formed, the gas barrier laminated film No. 16 was produced in the same manner as in Production Example 1.

&lt;Manufacturing Example 17&gt;

Except that the inorganic thin film layer was not formed, the gas barrier laminated film No. 17 was manufactured in the same manner as in Manufacturing Example 1.

&lt;Manufacturing Examples 18 to 20&gt;

Except that the coating liquid for forming a gas barrier resin composition layer was changed to coating liquid Nos. 11 to 13 for forming a gas barrier resin composition layer, the gas barrier laminated film No. was produced in the same manner as in Production Example 1. . 18 to 20.

&lt;Manufacturing Example 21&gt;

Except that the thickness of the gas barrier resin composition layer was changed to 0.01 μm, the gas barrier laminated film No. 21 was produced in the same manner as in Production Example 1.

&lt;Manufacturing example 22&gt;

Except that the thickness of the adhesion-promoting coating layer was changed to 0.01 μm, the gas barrier laminated film No. 22 was produced in the same manner as in Production Example 1.

&lt;Manufacturing Example 23&gt;

Except that the thickness of the gas barrier resin composition layer was changed to 0.7 μm, the gas barrier laminated film No. 23 was produced in the same manner as in Production Example 1.

The composition of the produced gas barrier laminated film Nos. 1 to 23 and the evaluation results are shown in Tables 1 and 2.

<tables><img alt="" file="twi508858b_d0001.tif" he="1675" id="" img-content="drawing" img-format="tif" inline="no" orientation="portrait" wi="2977" /></tables>

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Gas barrier laminated film Nos. 1 to 15, 22 are those that meet the requirements of the present invention. These films have high laminate strength and low oxygen permeability and water vapor permeability even after sterilization. Among them, the gas barrier laminate film No. 1 to 15 having a thickness of 0.3 μm between the inorganic film layer and the gas barrier resin composition layer has a thickness of 0.3 μm. The laminate strength after sterilization is superior.

Gas-barrier laminated film No. 16 has no gas-barrier resin composition layer, gas-barrier laminated film No. 17 has no inorganic film layer, and gas-barrier laminated film No. 18 has gas barrier properties When the resin composition does not contain an inorganic layered compound, any of these have high values of oxygen permeability and water vapor permeability.

The gas barrier laminated film No. 19 is a case where PVA is used as the gas barrier resin. During the sterilization process, the gas barrier laminated film and the unstretched polypropylene film will peel off. Gas-barrier laminated film No. 20 is a case where the gas-barrier resin composition does not contain additives, and its oxygen permeability and water vapor permeability before sterilization are high, and the laminate strength is very weak.

The gas barrier laminated film No. 21 is a case where the thickness of the gas barrier resin composition layer is thinner than 0.05 μm, and the oxygen permeability after sterilization treatment increases, that is, the gas barrier performance after sterilization treatment decreases. The gas barrier laminated film No. 23 is a case where the thickness of the gas barrier resin composition layer exceeds 0.5 μm, but the laminated strength after sterilization is very weak.

[Industrial Utilization Possibility]

According to the present invention, it is possible to obtain a gas-barrier laminated film that not only has high gas barrier properties against oxygen, water vapor, etc., but also has high interlayer adhesion and superior laminate strength. In particular, even after sterilization treatment, gas barrier properties can be obtained, the reduction of layer indirect force is small, and the gas barrier laminate film is suitable for various applications and has high practicality. In addition, it can also be made into a gas barrier laminated film with superior production stability and easy to obtain homogeneous properties.

The gas barrier film of the present invention is not only used in food packaging for sterilization, but also can be widely used in packaging applications of various foods, medicines, and industrial products, under high temperature and high humidity environments or requiring long-term stable gas barrier properties and durability. Industrial applications such as solar cells, electronic paper, organic EL (electroluminescence) devices, and semiconductor devices.