JP4439967B2 - Gas barrier film and gas barrier laminate using the same - Google Patents

Description

The present invention relates to a gas barrier film and a gas barrier laminate using the same, and more specifically, a gas barrier film formed by forming an inorganic thin film on a plastic film, and has good adhesion between the inorganic thin film and the plastic film. Therefore, it has excellent gas barrier properties, and even when subjected to hot water treatment (boil treatment, retort treatment, sterilization treatment), the gas barrier properties are maintained, and a gas barrier film suitable for packaging foods, pharmaceuticals, etc. and a gas barrier using the same The present invention relates to a conductive laminate.

Inorganic thin film can be selected from metals and / or metal oxides as the material for forming the thin film, thereby providing gas barrier properties, moisture impermeability, visible / ultraviolet light blocking properties, heat ray reflectivity, conductivity, and transparent conductivity. Therefore, it is used for various purposes because various properties such as magnetic properties and magnetic recording properties can be changed. For example, it is used for packaging materials, decorative materials, window glass blocking materials, gold / silver thread materials, capacitor materials, display materials, wiring board materials, magnetic recording materials, and the like. Furthermore, in recent years, attention has also been paid to new applications such as liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, electroluminescence (EL) substrates, part of transparent conductive sheets used in color filters and the like.
In recent years, many highly transparent gas barrier films in which an inorganic thin film made of silicon oxide, aluminum oxide, magnesium oxide or the like is formed on the surface of a substrate made of a plastic film have been proposed and put into practical use. However, such a gas barrier film has a problem in that the gas barrier property is deteriorated by causing partial destruction and peeling of the inorganic thin film during the film processing step or by contact with moisture. In particular, a gas barrier film formed with an inorganic thin film is desired to be used for hot water treatment (boil treatment, retort treatment, sterilization treatment), and maintaining the gas barrier property after the hot water treatment is an important issue.

Conventionally, in order to prevent a decrease in gas barrier properties, a method has been proposed in which a coating layer made of various polyurethanes, various polyesters or a mixture of polyurethane and polyester is provided between a substrate made of a polyester film and a vapor-deposited inorganic thin film layer. (For example, refer to Patent Document 1). Furthermore, in order to improve water-resistant adhesion and solvent resistance, a coating liquid containing a special polyurethane, polyester and epoxy compound has been proposed (for example, see Patent Document 2).
Also, a plastic film that uses an aqueous coating solution in consideration of the environment and safety and has heat-resistant and water-resistant adhesive properties, and the coating solution contains an aqueous crosslinking agent (see, for example, Patent Documents 3, 4, and 5) And a film (for example, see Patent Document 6) in which an inorganic thin film is formed on the surface of such a plastic film coating layer.
However, market demands for gas barrier properties after hydrothermal treatment and gas barrier properties after printing with solvent-based inks are increasing year by year, and inorganic thin films having more stable and high gas barrier properties are desired. Yes.

JP-A-2-50837 Japanese Patent Laid-Open No. 4-176858 JP-A-8-332706 JP 2001-58383 A JP 2001-79994 A JP 2003-320610 A

The present invention has been made in view of the above circumstances, and uses a gas barrier film excellent in adhesion between a plastic film as a base material and an inorganic thin film and a gas barrier property after hot water treatment or after printing, and the gas barrier film. An object of the present invention is to provide a gas barrier laminate.

As a result of various investigations for achieving the above object, the inventors of the present invention have developed a specific water-soluble and / or water-dispersible resin and a crosslinkable component in a gas barrier film having an inorganic thin film provided on the surface of the coating layer. It is found that a gas barrier film having excellent characteristics can be obtained by forming a coating layer with a coating solution containing a water-soluble and / or water-dispersible carbodiimide group-containing resin, and the present invention is based on this finding. It came to complete.
That is, the present invention provides the following gas barrier film and a gas barrier laminate using the gas barrier film.

1. In a gas barrier film in which a coating layer is formed on at least one surface of a plastic film and an inorganic thin film is provided on the surface of the coating layer, the coating layer is selected from a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin. At least one selected from water-soluble polyurethane resins, water-dispersible polyurethane resins, water-soluble polyester resins and water-dispersible polyester resins, water-soluble carbodiimide group-containing resins and / or water-dispersible carbodiimide group-containing resins And a gas barrier film characterized by having an oxygen permeability measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH of 10 fmol / m ² / s / Pa or less.
2. 2. The gas barrier film as described in 1 above, wherein the content of the water-soluble polyacrylic resin and / or the water-dispersible polyacrylic resin in the coating layer is 10 to 50% by mass based on the resin constituting the coating layer.
3. The laminate obtained by laminating an unstretched polypropylene film having a thickness of 60 μm on the inorganic thin film had an oxygen permeability of 10 fmol / m ² / s / Pa or less measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH. The oxygen permeability rate (measurement conditions are the same as above) after performing hydrothermal treatment at 120 ° C. for 30 minutes on the laminate is 50 fmol / m ² / s / Pa or less. 3. The gas barrier film according to 1 or 2 .
4). 4. The gas barrier film as described in 1 or 3 above, wherein a heat treatment at 50 ° C. or higher is performed after the inorganic thin film is formed.
5. The coating layer is a water-soluble polyurethane resin, a water-dispersible polyurethane resin, a water-soluble polyester resin, and a water-dispersible polyester resin, a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, 5. The gas barrier film as described in any one of 1 to 4 above , which comprises a carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin.

6). The coating layer comprises a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, a water-soluble polyurethane resin and / or a water-dispersible polyurethane resin, a water-soluble polyester resin and / or a water-dispersible polyester resin, 6. The gas barrier film as described in any one of 1 to 5 above, which comprises a carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin.
7). 7. The gas barrier film according to any one of 1 to 6 above, wherein the inorganic thin film contains silicon oxide.
8). 8. Any one of said 1 thru | or 7 whose content rate of water-soluble carbodiimide group containing resin in a coating layer and / or water-dispersible carbodiimide group containing resin is 10-50 mass% on the resin basis which comprises a coating layer. Gas barrier film.
9. 9. The gas barrier film according to any one of 1 to 8 above, wherein the water-soluble polyacrylic resin and / or water-dispersible polyacrylic resin does not contain an emulsifier.
10. 10. The gas barrier film as described in any one of 1 to 9 above, wherein the plastic film contains one or more plastics selected from polyester, polypropylene, polyamide, polyvinyl alcohol, and ethylene-vinyl acetate copolymer partial hydrolyzate.
11. 11. The gas barrier film as described in 10 above, wherein 10 to 100% by mass of the plastic constituting the plastic film is a recycled plastic.

12 12. The gas barrier film according to any one of 1 to 11 above, wherein the coating layer is formed by applying a coating solution to a plastic film and then stretching in at least one direction.
13. Gas barrier film according to any one of the above 1 to 1 2 in the inorganic thin film surface formed by providing a resin-containing layer.
14 14. The gas barrier film according to any one of 1 to 3 and 5 to 13 , which is formed by performing a heat treatment at 50 ° C. or higher after forming an inorganic thin film.
15. A gas barrier laminate comprising a print layer formed on the surface of the inorganic thin film of the gas barrier film according to any one of 1 to 14 and a heat seal layer laminated on the surface of the print layer. body.
16. The gas barrier laminate as described in 15 above, wherein at least one layer selected from paper and a plastic film is laminated between the printing layer and the heat seal layer.
17. The gas barrier laminate according to the above 15 or 16 , wherein the laminate is subjected to a heat treatment at 50 ° C. or higher after the laminate is formed.
18. A gas barrier laminate in which a plastic film is laminated on an inorganic thin film of the gas barrier film described in any one of 1 to 14 above, and is subjected to a heat treatment at 50 ° C. or more after the plastic film is laminated. A gas barrier laminate characterized by the above.
19. In a gas barrier laminate in which a plastic film is laminated on an inorganic thin film of the gas barrier film according to any one of 1 to 14 above, the oxygen permeability measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH 10 fmol / m ² / s / Pa or less, and the oxygen permeability (measurement conditions are the same as above) after the hydrothermal treatment at 120 ° C. for 30 minutes is 50 fmol / m ² / day / A gas-barrier laminate having a Pa or less.
20. The gas barrier laminate according to the above item 19 , wherein a heat treatment at 50 ° C. or higher is performed after the laminate is formed.
21. In a gas barrier laminate in which a printing layer is formed on the inorganic thin film surface of the gas barrier film according to any one of 1 to 14 above and a heat seal layer is laminated on the surface of the printing layer, the temperature is 25 ° C., Oxygen permeability measured under conditions of humidity 80% RH is 10 fmol / m ² / s / Pa or less, and oxygen permeability after hydrothermal treatment of the laminate for 30 minutes at 120 ° C. (Measurement conditions are the same as above) is 50 fmol / m ² / day / Pa or less, a gas barrier laminate.
22. The gas barrier laminate as described in 21 above, wherein at least one layer selected from paper and plastic film is laminated between the printing layer and the heat seal layer.
23. The gas barrier laminate according to the above 21 or 22 , wherein the laminate is subjected to a heat treatment at 50 ° C. or higher after the laminate is formed.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier film excellent in the adhesiveness and gas barrier property between the plastic film which is a base material, and an inorganic thin film, especially the gas barrier property after a retort process and after printing, and a gas barrier property laminated body using the same The industrial value of the present invention is very large.

Hereinafter, the present invention will be described in detail. The material for the plastic film used as a base material in the present invention (hereinafter sometimes referred to as “base film”) is not particularly limited as long as it is a resin used in a normal packaging material. Specific examples include polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefins, polyester resins such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6 , Nylon 66, nylon 12, polyamide such as copolymer nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, Examples include polycarbonate (PC), polyvinyl butyral, polyarylate, fluorine-based resin, acrylate resin, and biodegradable resin. These can be used individually by 1 type or in combination of 2 or more types. Among these, polyester, polypropylene, polyamide, polyvinyl alcohol, and ethylene-vinyl acetate copolymer partial hydrolyzate are preferable, and polyester and polyamide are particularly preferable.

Polyester that is particularly suitable as a raw material for the base film used in the present invention includes polyethylene terephthalate in which 80 mol% or more of the structural unit is ethylene terephthalate, and polyethylene in which 80 mol% or more of the structural unit is ethylene naphthalate. Examples thereof include naphthalate and poly-1,4-cyclohexanedimethylene terephthalate in which 80 mol% or more of the structural unit is 1,4-cyclohexanedimethylene terephthalate.
Examples of copolymer components other than the above-described constituent components include diol components such as diethylene glycol, propylene glycol, neopentyl glycol, polyethylene glycol, and polytetramethylene glycol, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5- Sodium disulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid and dicarboxylic acid component of ester-forming derivative thereof, hydroxybenzoic acid and hydroxymonocarboxylic acid component of ester-forming derivative thereof, and the like can be used.

Polyamides that are particularly suitable as raw materials for the base film used in the present invention include aliphatic polyamides and aromatic polyamides. Examples of the aliphatic polyamide include a ring-opening polymer of cyclic lactam, a self-polycondensation product of aminocarboxylic acid, a polycondensation product of dicarboxylic acid and diamine, and the like. Specific examples include a homopolymer of ε-caprolactam referred to as nylon 6, polyhexamethylene adipamide referred to as nylon-66, and the like.
The aromatic polyamide is a polyamide having an aromatic ring, and the aromatic polyamide used in the present invention is not particularly limited, but is composed of xylylenediamine and an α, ω aliphatic dicarboxylic acid having 6 to 12 carbon atoms. An aromatic polyamide containing 70 mol% or more of the polyamide structural unit in the molecular chain is preferably used. Specific examples of the polyamide component composed of xylylenediamine and an α, ω aliphatic dicarboxylic acid having 6 to 12 carbon atoms include polymetaxylylene adipamide, polymetaxylylene pimeramide, polymetaxylylene azelamide, Examples include homopolymers such as polyparaxylylene azelamide and polyparaxylylene decanamide, and copolymers such as metaxylylene / paraxylylene adipamide copolymer and metaxylylene / paraxylylene sebacamide copolymer. .

  Other polyamide constituents include nylon salts of diamines and dicarboxylic acids, ring-opening polymers of lactams such as ε-caprolactam, and self-polycondensates of ω-aminocarboxylic acids such as ε-aminocarboxylic acid. Is mentioned. Specific examples of diamines as components of nylon salts include aliphatic diamines such as hexamethylene diamine and 2,2,4-trimethylhexamethylene diamine, heterocycles such as piperazine bispropylamine and neopentylglycolpropylamine. Or a hetero atom containing diamine etc. are mentioned. Specific examples of the dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and cyclic aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. An acid etc. are mentioned.

As a raw material of the base film used in the present invention, there is no particular problem even if it is a recycled raw material. For example, from the viewpoint of resource saving, recycled plastic processed into scrap film chips generated in the manufacturing process of plastic film products. May be used. The ratio of the recycled plastic used is not particularly limited, but is preferably in the range of 10 to 100% by mass as the ratio in the raw material plastic.
When using recycled materials, it is necessary to pay attention to the fact that low molecular weight components such as oligomers and additives of plastic film materials are deposited on the surface of the plastic film during the manufacturing process and secondary processing of the gas barrier film and its laminate. Become. In that case, the coating layer in this invention also plays the role of those precipitation prevention.

The base film used in the present invention may contain additive particles that form protrusions on the film surface, precipitated particles, and other catalyst residues within a range of amounts that are usually used depending on the application. Further, as necessary, additives other than the above-mentioned protrusion-forming agent may be used as an antistatic agent, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, an antioxidant, and a colorant as long as the effects of the present invention are not impaired. Further, it may contain a light blocking agent, an ultraviolet absorber and the like.
The base film used in the present invention may be any of a single layer film mainly using one of the above raw materials, a blend single layer film using two or more types of raw materials, and a co-extrusion laminated film. In the case of a co-extrusion laminated film, the structure of each layer may be one using one type of raw material or a blend layer using two or more types.

The base film may be an unstretched film or a stretched film. Moreover, the film which laminated | stacked 2 or more types of plastic films may be sufficient. The base film can be produced by a conventionally known general method. For example, an unstretched film that is substantially amorphous and not oriented can be produced by melting a raw material resin with an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. The unstretched film is subjected to a film flow (vertical axis) direction or a film by a conventionally known general method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. A stretched film stretched in at least a uniaxial direction can be produced by stretching in the direction perpendicular to the flow direction (horizontal axis).
The thickness of the base film used in the present invention is appropriately selected according to the use such as mechanical strength, flexibility, transparency, etc. as the base material in the present invention, and is usually about 2 to 500 μm, preferably 5 to 200 μm. Selected for the range. The base film includes sheets having a relatively large thickness. Moreover, the width | variety and length of a base film do not have a restriction | limiting in particular, According to a use, it can select suitably.

In the present invention, the coating layer formed on the base film needs to contain a water-soluble carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin as a crosslinkable resin.
Water-soluble carbodiimide group-containing resins or water-dispersible carbodiimide group-containing resins are less toxic and reactive than aqueous crosslinkable components such as aziridine, block isocyanate, water-dispersible isocyanate, methylolated melamine, aqueous epoxy, oxazoline, etc. It is excellent in terms of overall height, pot life, and low reaction temperature, and is suitable as a crosslinkable component of a coating solution for forming a coating layer of a gas barrier film. In particular, the heat-resistant water gas barrier property, which is improved by performing a heat treatment after forming an inorganic thin film on the surface of the coating layer or after forming a gas barrier laminate described later, is obtained by adding a carbodiimide group-containing resin to the coating solution. Effectively brought about.

The carbodiimide-containing resin is a general term for resins having at least two so-called carbodiimide groups represented by the following general formula (1) per molecule, and is obtained by polycondensation of a diisocyanate compound in the presence of a catalyst.
-N = C = N- (1)
As a method for producing a carbodiimide group-containing resin, a known technique can be applied. For example, the methods described in Japanese Patent Publication No. 47-33279 and Japanese Patent Laid-Open No. 9-235508 can be applied. Examples of the diisocyanate compound that is a starting material for the carbodiimide group-containing resin include aromatic, aliphatic, and alicyclic diisocyanates. Specific examples include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexyl diisocyanate.

In the range not impairing the effects of the present invention, in order to further improve the water solubility and / or water dispersibility of the carbodiimide group-containing resin, any surfactant, polyalkylene oxide, quaternary ammonium salt of dialkylamino alcohol, Hydrophilic monomers such as hydroxyalkyl sulfonates can be added. The amount of these compounds added is usually about 1 to 10 parts by mass with respect to 100 parts by mass of the water-soluble carbodiimide group-containing resin and / or the water-dispersible carbodiimide group-containing resin.
The content of the water-soluble carbodiimide group-containing resin and / or the water-dispersible carbodiimide group-containing resin in the coating layer is preferably 5 to 50% by mass, more preferably 15 to 30% by mass based on the resin constituting the coating layer. is there. When the content ratio of the carbodiimide group-containing resin is 10% by mass or more, crosslinking is sufficient, and when it is 50% by mass or less, the balance between cost and effect is good.

In the coating layer, in addition to a water-soluble carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin, a water-soluble polyacrylic resin, a water-dispersible polyacrylic resin, a water-soluble polyurethane resin, a water-dispersible polyurethane resin, 1 or more types chosen from water-soluble polyester resin and water-dispersible polyester resin are contained. The water-soluble polyacrylic resin or water-dispersible polyacrylic resin is a resin mainly composed of alkyl acrylate and / or alkyl methacrylate. Specifically, the content ratio of the alkyl acrylate and / or alkyl methacrylate component is usually 40. It is a water-soluble resin or a water-dispersible resin in which the content of the vinyl monomer component that is copolymerizable and has a functional group is usually about 5 to 60 mol%.
Examples of the functional group in the vinyl monomer include a carboxyl group, an acid anhydride group, a sulfonic acid group or a salt thereof, an amide group or an alkylolated amide group, an amino group (including a substituted amino group), Examples thereof include an alkylolated amino group or a salt thereof, a hydroxyl group, and an epoxy group, and a carboxyl group, an acid anhydride group, an epoxy group, and the like are particularly preferable. Two or more of these groups may be contained in the polyacrylic resin.

  In the above-mentioned water-soluble polyacrylic resin or water-dispersible polyacrylic resin, by making the content of alkyl acrylate and / or alkyl methacrylate 40 mol% or more, coating properties, coating strength, and blocking resistance are particularly good. It becomes. Then, alkyl acrylate and / or alkyl methacrylate is 95 mol% or less, and a compound having a specific functional group as a copolymerization component is introduced into water-soluble polyacrylic resin and / or water-dispersible polyacrylic resin by 5 mol% or more. Thus, water-solubilization or water-dispersion can be facilitated and the state can be stabilized over a long period of time. As a result, it is possible to improve the adhesion between the coating layer and the substrate film, and improve the strength, water resistance, and chemical resistance of the coating layer due to the reaction in the coating layer.

  Examples of the alkyl group of the above alkyl acrylate and alkyl methacrylate include methyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 2-ethylhexyl group, lauryl group, stearyl group, cyclohexyl group and the like. It is done. Examples of the compound having a carboxyl group or an acid anhydride include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and the like, and alkali metal salts, alkaline earth metal salts, ammonium salts, and the like. Maleic acid is mentioned. Examples of the compound having a sulfonic acid group or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, metal salts such as sodium salts of these sulfonic acids, ammonium salts, and the like.

Examples of the compound having the amide group or alkylolated amide group include acrylamide, methacrylamide, N-methyl methacrylamide, methylol acrylamide, methylol methacrylamide, ureido vinyl ether, β-ureido isobutyl vinyl ether, and ureido. Examples include ethyl acrylate.
Examples of the compound having an amino group or an alkylolated amino group or a salt thereof include diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate. Dimethylaminoethyl vinyl ether, compounds in which those amino groups are methylolated, compounds quaternized with alkyl halides, dimethyl sulfate, sultone and the like.

  Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, β-hydroxyvinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl. Examples include vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

Furthermore, examples of compounds that can be used in combination with these monomers include acrylonitrile, styrenes, butyl vinyl ether, maleic acid mono- or dialkyl esters, fumaric acid mono- or dialkyl esters, itaconic acid mono- or dialkyl esters, methyl vinyl ketone, Examples include vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, and vinyl trimethoxysilane.

The water-soluble polyacrylic resin or water-dispersible polyacrylic resin may be any type of polyacrylic resin and may contain any emulsifier as long as the effects of the present invention are not impaired. A polyacrylic resin that does not contain an emulsifier is preferably used.
Therefore, the water-soluble polyacrylic resin or water-dispersible polyacrylic resin used in the present invention may be a self-dispersing type polyacrylic resin synthesized using a reactive emulsifier, and a high molecular weight surfactant is used. It may be a polyacrylic resin synthesized by use. Further, the water-soluble polyacrylic resin or the water-dispersible polyacrylic resin may be a self-crosslinking resin.

  The content ratio of the water-soluble polyacrylic resin and / or the water-dispersible polyacrylic resin in the coating layer is usually in the range of 5 to 80% by mass, preferably 10 to 50% by mass, based on the resin constituting the coating layer. . When the content ratio of the polyacrylic resin is 5% by mass or more, a sufficient effect of preventing the oligomer precipitation of the plastic film by the coating layer is obtained, and when it is 80% by mass or less, the adhesiveness to the inorganic thin film is good. Become. The water-soluble polyacrylic resin and / or water-dispersible polyacrylic resin is preferably used in combination with a water-soluble polyurethane resin and / or a water-dispersible polyurethane resin described later.

  The water-soluble polyurethane resin or water-dispersible polyurethane resin used in the present invention is not particularly limited, but those that do not contain a low-molecular hydrophilic dispersant are preferably used. The water-soluble polyurethane resin or water-dispersible polyurethane resin is a water-soluble resin or water-dispersible resin produced by reacting a polyhydroxy compound and a polyisocyanate compound according to a conventional method. The water-soluble polyurethane or water-dispersible polyurethane resin preferably contains a carboxyl group or a salt thereof (hereinafter simply abbreviated as a carboxyl group) in order to increase the affinity with an aqueous medium.

Examples of the polyhydroxy compound include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone, Polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, glycerin and the like can be mentioned.
Examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, an adduct of tolylene diisocyanate and trimethylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane, and the like.

The introduction of a carboxyl group into the polyurethane side chain is, for example, using a carboxyl group-containing polyhydroxy compound as one of the raw material polyhydroxy compounds in the synthesis of polyurethane, or an isocyanate group of a polyurethane having an unreacted isocyanate group. It can be easily carried out by a method of reacting a hydroxyl group-containing carboxylic acid or an amino group-containing carboxylic acid and then neutralizing the reaction product by adding it to an alkaline aqueous solution under high-speed stirring.
Examples of the carboxyl group-containing polyhydroxy compound include dimethylolpropionic acid, dimethylolacetic acid, dimethylolvaleric acid, trimellitic acid bis (ethylene glycol) ester, and the like. Examples of the hydroxyl group-containing carboxylic acid include 3-hydroxypropionic acid, γ-hydroxybutyric acid, p- (2-hydroxyethyl) benzoic acid, and malic acid. Examples of the amino group-containing carboxylic acid include β-amino acid. Examples include propionic acid, γ-aminobutyric acid, and p-aminobenzoic acid.

The carboxyl group of the water-soluble polyurethane resin or water-dispersible polyurethane resin may have a counter ion, and such a counter ion is usually a monovalent ion, preferably an amine-based onium ion containing a hydrogen ion or an ammonium ion. Is mentioned. The water-soluble polyurethane resin or water-dispersible polyurethane resin may be a self-crosslinking resin.
The blending ratio of the water-soluble polyurethane resin and / or water-dispersible polyurethane resin in the coating layer is usually about 5 to 80% by mass, preferably 10 to 70% by mass, based on the resin constituting the coating layer. When the content ratio of the water-soluble polyurethane resin and / or water-dispersible polyurethane resin is 5% by mass or more, the inorganic thin film is prevented from being peeled off together with the coating layer, and when it is 80% by mass or less, the heat resistant water adhesiveness is It becomes good. The water-soluble polyurethane resin and / or water-dispersible polyurethane resin is preferably used in combination with a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin.

Although it does not restrict | limit especially as water-soluble polyester resin or water-dispersible polyester resin, Preferably it is a polyester resin which does not contain a low molecular hydrophilic dispersing agent etc., Either saturated polyester or unsaturated polyester can be used.
Examples of the dicarboxylic acid component of the saturated polyester include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid and sebacic acid, and hydroxybenzoic acid. Examples thereof include hydroxycarboxylic acids such as acids and ester-forming derivatives thereof. Examples of the glycol component include aliphatic glycols such as ethylene glycol, 1,4-butanediol, diethylene glycol, and triethylene glycol, alicyclic glycols such as 1,4-cyclohexanedimethanol, and aromatics such as p-xylylenediol. Group diol, polyethylene glycol, polypropylene glycol, poly (oxyalkylene) glycol such as polytetramethylene glycol, and the like.

  The saturated polyester has a linear structure, but a branched polyester can also be obtained by using a trivalent or higher valent ester-forming component. On the other hand, as said unsaturated polyester, what is shown by following (1) and (2) is mentioned, for example.

(1) It is disclosed in Japanese Patent Publication No. 45-2201, Japanese Patent Publication No. 46-2050, Japanese Patent Publication No. 44-7134, Japanese Patent Publication No. 48-78233, Japanese Patent Publication No. 50-58123, etc. An unsaturated polyester having a copolymerizable unsaturated group in a resin skeleton obtained by reacting a raw material component containing a copolymerizable unsaturated group with another raw material component.
(2) After obtaining a saturated polyester having no copolymerizable unsaturated group as disclosed in JP-B-49-47916, JP-B-50-6223 and the like, hydroxyl groups present in the saturated polyester or An unsaturated polyester obtained by adding a vinyl monomer having a functional group reactive with a functional group such as a carboxyl group and a vinyl group to a saturated polyester.

  Examples of the vinyl monomer include compounds having an epoxy group and a vinyl group such as glycidyl methacrylate, compounds having an alkoxysilanol group and a vinyl group such as vinylmethoxysilane and methacryloxyethyltrimethoxysilane, maleic anhydride, tetrahydro Examples include compounds having an acid anhydride group such as phthalic anhydride and a vinyl group, and compounds having an isocyanate group and a vinyl group such as 2-hydroxypropyl methacrylate-hexamethylene diisocyanate adduct.

  The water-soluble polyester resin or water-dispersible polyester resin preferably contains a carboxyl group in order to increase the affinity with an aqueous medium. Introducing a carboxyl group into the side chain of a saturated or unsaturated polyester is a method in which a dioxane compound having a carboxylic acid is reacted with the polyester (Japanese Patent Laid-Open No. 61-228030), and the unsaturated carboxylic acid is radically grafted onto the polyester. A method of introducing a substituent into an aromatic ring by reacting a polyester with halogenoacetic acid (Japanese Patent Laid-Open No. 62-225527), a polyester and a polyvalent carboxylic anhydride compound Can be easily carried out by a method such as a method of reacting with (JP-A-62-240318).

The carboxyl group of the water-soluble polyester resin or water-dispersible polyester resin may have a counter ion, and as such a counter ion, usually a monovalent ion, preferably an amine-based onium ion containing a hydrogen ion or an ammonium ion. Can be mentioned.
The content ratio of the water-soluble polyester resin and / or water-dispersible polyester resin in the coating layer is usually in the range of 3 to 70% by mass and preferably 5 to 30% by mass on the basis of the resin constituting the coating layer. When the content ratio of the water-soluble and / or water-dispersible polyester resin is 3% by mass or more, the gas barrier property is good, and when it is 70% by mass or less, the gas barrier property after the hot water treatment is good.

  In the gas barrier film of the present invention, the coating layer can be formed by coating a coating solution containing the resin on a base film. The coating solution can be used as a crosslinkable component to improve the adhesiveness (blocking property), water resistance, solvent resistance, mechanical strength, etc. of the coating layer, for example, an epoxy-based, methylolized or alkylolized urea system, Compounds such as melamine, guanamine, acrylamide, and polyamide, aziridine compounds, block polyisocyanate compounds, oxazoline group-containing compounds, silane coupling agents, titanium coupling agents, zirco aluminate coupling agents, peroxides, A small amount of a photoreactive vinyl compound or a photosensitive resin may be contained within a range in which the adhesiveness is not deteriorated. In particular, the use of an epoxy compound such as glycidyl acrylate or glycidyl methacrylate is preferable because it can be cross-linked to a side chain such as a carboxyl group in the resin compound to enhance the adhesion to the inorganic thin film.

  In order to improve the adhesion and slipperiness, the coating solution is, for example, silica, silica sol, alumina, alumina sol, zirconium sol, kaolin, talc, calcium carbonate, titanium oxide, barium salt, carbon black, sulfide. It may contain molybdenum, antimony oxide sol, etc., and further, if necessary, defoaming agent, applicability improver, thickener, antistatic agent, organic lubricant as long as the effects of the present invention are not impaired. Organic polymer particles, antioxidants, ultraviolet absorbers, foaming agents, dyes, pigments and the like may be contained.

As a method of applying the coating solution to the base film, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater or other coatings shown in “Coating system” (Yuji Harasaki, Tsuji Shoten, published in 1979) Application is performed within the substrate film manufacturing process using an apparatus. The coating layer may be formed after the base film is formed, but is preferably formed in the base film forming step. When the base film is a biaxially stretched film, the coating liquid is preferably applied to the base film stretched uniaxially in the longitudinal direction, stretched in the transverse direction in a dry or undried state, and then subjected to heat treatment. It is preferable to form a coating layer.
The above-mentioned method can be carried out simultaneously with film formation, application and drying, and therefore has a great merit in terms of production cost, and is particularly preferably employed. The coating layer can be provided on one side or both sides of the base film. When the coating layer is provided on both sides of the base film, these coating layers may be the same or different. In addition, in order to improve the applicability | paintability and adhesiveness to a base film, you may perform a chemical process, an electrical discharge process, etc. on the surface of a base film before apply | coating a coating liquid.

In the present invention, as described above, the thickness of the base film is usually about 2 to 500 μm, preferably 5 to 200 μm. The thickness of the coating layer is generally about 0.01 to 5 μm, preferably 0.02 to 1 μm. When the thickness of the coating layer is 0.01 μm or more, a uniform coating layer can be obtained, and when it is 5 μm or less, the slipperiness is improved and the base film can be easily handled.
Further, the water droplet contact angle of the coating layer formed as described above is preferably 60 ° or more. In general, a water-soluble resin coating layer having many emulsifiers, hydrophilic compounds, and hydrophilic groups requires a caution because it tends to lower the water droplet contact angle and deteriorate the water-resistant adhesion to the inorganic thin film.

In the present invention, examples of the inorganic substance constituting the inorganic thin film include aluminum, silicon, magnesium, palladium, zinc, tin, nickel, silver, copper, gold, indium, stainless steel, chromium, titanium, and other metals, and the like. The oxide of each metal or a mixture thereof is mentioned. Diamond-like carbon mainly composed of silicon oxide, aluminum oxide, and hydrocarbon is preferable. In particular, silicon oxide is most preferable in that the effect of heat treatment described later is remarkably exhibited and high gas barrier properties can be stably maintained.
Methods for forming the inorganic thin film include a vapor deposition method and a coating method, and are not particularly limited. However, the vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained. Examples of the deposition method include methods such as vacuum deposition, ion plating, sputtering, and CVD (chemical vapor deposition). The inorganic thin film is formed on the surface of the coating layer. Although the thickness of an inorganic thin film is suitably selected according to the end use of a gas barrier film, it is about 0.1-500 nm normally, Preferably it is 0.5-50 nm. By setting the thickness to 0.1 nm or more, a sufficient gas barrier property can be obtained, and by making it not too thick, the inorganic thin film does not crack or peel off, and the transparency is maintained.

Substrate film, a gas barrier film composed of the coating layer and the inorganic thin film, from the viewpoint of obtaining a good gas barrier properties, temperature 25 ° C., the oxygen permeability was measured under the conditions of RH 80% humidity is 10 fmol / m ² / It needs to be s / Pa or less.
In addition, the gas barrier film composed of the base film, the coating layer and the inorganic thin film is formed by laminating an unstretched polypropylene film having a thickness of 60 μm on the inorganic thin film in order to maintain a good gas barrier property even after the hot water treatment. In this case, the oxygen permeability of the laminate (measurement conditions are the same as above) is 10 fmol / m ² / s / Pa or less, and the laminate was subjected to hydrothermal treatment at 120 ° C. for 30 minutes. Later, the oxygen permeability (measurement conditions are the same) is required to be 50 fmol / m ² / s / Pa or less.
As the gas barrier film composed of the base film, the coating layer and the inorganic thin film, the following embodiments are preferable.

(1) The coating layer is a water-soluble polyacrylic resin, a water-dispersible polyacrylic resin, a water-soluble polyurethane resin, a water-dispersible polyurethane resin, a water-soluble polyester resin, and a water-dispersible polyester resin; A gas barrier film comprising a heat-resistant carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin and subjected to a heat treatment at 50 ° C. or higher after forming the inorganic thin film.
(2) The coating layer is a water-soluble polyurethane resin, a water-dispersible polyurethane resin, a water-soluble polyester resin and a polyester resin, a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, and a water-soluble A gas barrier film comprising a carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin.
(3) The coating layer includes a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, a water-soluble polyurethane resin and / or a water-dispersible polyurethane resin, a water-soluble polyester resin and / or a water-dispersible polyester resin. A gas barrier film comprising a water-soluble carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin.

The inorganic thin film in the gas barrier film of the present invention may be laminated with a resin-containing layer after forming the inorganic thin film in order to impart adhesiveness, particularly water-resistant adhesion, solvent resistance, and scratch resistance. The raw material used for forming this resin-containing layer is not particularly limited as long as it is a resin that is generally used. For example, polyester resin, urethane resin, isocyanate resin, acrylic resin, vinyl alcohol resin, EVOH, vinyl-modified resin, epoxy resin, cross-linking base-containing resin, modified styrene resin, modified silicon resin, etc. A mixture of more than one species can be used. Also, silica or alumina sol and particles or layered inorganic fine particles can be added and polymerized.
Furthermore, a silane coupling agent or an organic titanium compound is added to the resin-containing layer in order to improve adhesion to the inorganic thin film, and other known additives such as antistatic agents, light blocking agents, ultraviolet absorbers, etc. Further, a plasticizer, a filler, a colorant, a stabilizer, an antifoaming agent, a crosslinking agent, an antiblocking agent, an antioxidant and the like can be added as long as the effects of the present invention are not impaired.

The thickness of the resin-containing layer is usually about 0.05 μm to 5 μm, preferably 0.1 μm to 2 μm. When the resin layer thickness is 0.05 μm or more, the effect of imparting functionality is high, and when it is 5 μm or less, problems such as blocking do not occur.
In the gas barrier film of the present invention, it is preferable to perform a heat treatment at 50 ° C. or higher after forming the inorganic thin film. When forming a resin content layer on an inorganic thin film, this heat treatment is performed after forming a resin content layer. By performing such heat treatment, good gas barrier properties are maintained even after the hot water treatment. About heat processing, it demonstrates in the heating of the gas-barrier laminated body mentioned later.

The gas barrier laminate of the present invention is obtained by laminating various layers on the gas barrier film of the present invention, and can be a gas barrier laminate according to the application. A normal embodiment of the gas barrier laminate includes a gas barrier laminate in which a plastic film is laminated on the inorganic thin film (gas barrier layer). As a plastic film, the same film as the base film used for the gas barrier film of the present invention can be used.
By using a film made of a resin capable of heat sealing as the plastic film, heat sealing becomes possible, and it can be used as various containers. Examples of resins that can be heat sealed include known resins such as polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, acrylic resins, and biodegradable resins.
The thickness of the plastic film is appropriately selected according to the application such as mechanical strength, flexibility, transparency, etc. of the laminated structure of the present invention, but is usually about 5 to 500 μm, preferably in the range of 10 to 200 μm. is there. Further, the width and length of the film are not particularly limited, and can be appropriately selected according to the application.

  As another embodiment of the gas barrier laminate, there may be mentioned one in which a printing layer is formed on the surface of the inorganic thin film of the gas barrier film of the present invention and a heat seal layer is further laminated thereon. As the printing ink used for forming the printing layer, a printing ink containing an aqueous resin or a solvent-based resin can be used. Here, examples of the resin used for the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. In addition to printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. You may add a well-known additive in the range which does not impair the effect of this invention.

The printing method for providing the printing layer is not particularly limited, and a known printing method such as an offset printing method, a gravure printing method, a screen printing method, or the like can be used. For drying the solvent after printing, known drying methods such as hot air drying, hot roll drying, and infrared drying can be used.
Moreover, at least 1 layer chosen from paper and a plastic film can be laminated | stacked between a printing layer and a heat seal layer. As the plastic film, the same film as the plastic film substrate used in the gas barrier film of the present invention can be used. Among these, paper, polyester resin, polyamide resin, and biodegradable resin are preferable from the viewpoint of obtaining sufficient rigidity and strength of the laminate.
The thickness of the printing layer is usually about 0.05 to 5 μm, the thickness of the heat seal layer is usually about 1 to 200 μm, and the thickness of at least one layer selected from paper and plastic film is usually about 5 μm to 5 mm. can do.

In the gas barrier laminate of the present invention, from the viewpoint of maintaining good gas barrier properties even after hydrothermal treatment, various layers are laminated on the gas barrier film to form a laminate, followed by heating performed after forming the inorganic thin film described above. It is preferable to perform a heat treatment at 50 ° C. or higher as in the case of the treatment. In the case of heating after the formation of the laminated body, any of a method of heating the laminated body after being subjected to secondary processing into a form such as a bag or a container, and a method of heating after putting contents into these secondary processed products can be adopted.
The conditions for the heat treatment vary depending on the type and thickness of the elements constituting the gas barrier film or gas barrier laminate, but are not particularly limited as long as the method can maintain the required temperature for the required time. For example, a method of storing in an oven or temperature-controlled room set to the required temperature, a method of blowing hot air, a method of heating with an infrared heater, a method of irradiating light with a lamp, a direct contact with a hot roll or hot plate Examples are a method of imparting a light and a method of irradiating with microwaves. Moreover, even if it heat-processes after cut | disconnecting a film and a laminated body to the magnitude | size which is easy to handle, you may heat-process with a film roll. Furthermore, if necessary time and temperature can be obtained, a heating device may be incorporated in a part of a film production apparatus such as a coater or a slitter, and heating may be performed in the production process.

The temperature of the above heat treatment is not particularly limited as long as it is usually 50 ° C. or higher, and is not higher than the melting point of the plastic film used for the base film and laminate used, and the lower limit is preferably 60 ° C., and the upper limit is usually 200. It is about ℃, preferably 160 ℃. When the treatment temperature is less than 50 ° C., the treatment time required for the effect of the heat treatment to be manifested becomes extremely long, which is not realistic. The time for the heat treatment tends to be shortened as the treatment temperature increases. Further, when the treatment temperature is high, the gas barrier film and the gas barrier laminate may be thermally decomposed and the gas barrier property may be lowered, so that it is preferable to shorten the treatment time. For example, combinations of temperature and time such as 50 ° C. for 2 days to 6 months, 80 ° C. for 2 hours to 6 days, and 150 ° C. for 2 minutes to 60 minutes are possible. However, these are merely guidelines, and differ depending on the type and thickness of each layer constituting the gas barrier film or gas barrier laminate.
With respect to the optimum time for the heat treatment as described above, the following correlation equation is derived based on the experimental results. That is, the optimum heat treatment time t (sec) is shown below by the heat treatment temperature T (K).
3.0 × 10 ⁻¹⁰ × exp (11000 / T) <t <2.4 × 10 ⁻¹⁰ × exp (13500 / T)

The gas barrier laminate of the present invention has an oxygen permeability of 10 fmol / m ² / s / measured under the conditions of a temperature of 25 ° C. and a humidity of 80% RH in order to maintain good gas barrier properties even after hydrothermal treatment. The oxygen permeability (measurement conditions are the same as above) after the hydrothermal treatment at 120 ° C. for 30 minutes is 50 fmol / m ² / s / Pa or less. Cost. When the oxygen permeability is 50 fmol / m ² / s / Pa or less, good gas barrier properties can be maintained even after a boil treatment, a retort treatment, a sterilization treatment, or the like.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, about the gas-barrier film or gas-barrier laminated body obtained in the Example etc., any one of the following (A), (B), and (C) was performed.

(A) Untreated; gas barrier film or gas barrier laminate as it is.
(B) Printing treatment: Gravure ink (“NEW LP Super White” manufactured by Toyo Ink) is diluted in half with diluent SL302 (toluene, methyl ethyl ketone, isopropyl alcohol mixed solution) on the inorganic thin film surface of the gas barrier film, and the thickness is 2 μm. Printed.
(C) Retort treatment: The gas barrier laminate was retorted at 120 ° C. for 30 minutes with a retort tester (PL30AERIII manufactured by Hirayama Seisakusho).

Moreover, the following evaluation was performed about the gas-barrier laminated body obtained in the Example etc.
(1) Water vapor transmission rate (g / m ² / day)
(I) Measurement was performed on an untreated gas barrier laminate. The measurement was performed under the conditions of a temperature of 40 ° C. and a humidity of 90% RH with a water vapor transmission rate measuring device (“W-1 type moisture permeability measuring device” manufactured by Modern Controls). The water vapor transmission rate was determined according to the following criteria.
A: 2 or less B: Greater than 2 and 10 or less C: Greater than 10

(2) Oxygen permeability (fmol / m ² / s / Pa)
It measured about the gas-barrier laminated body which performed (a) unprocessed, (c) printing process, and (b) retort process separately. It was measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH with an oxygen transmission rate measurement device (“OX-TRN100 type oxygen transmission rate measurement device” manufactured by Modern Controls). The oxygen transmission rate was determined according to the following criteria.
A: 10 or less B: Greater than 10 and 50 or less C: Greater than 50

(1) Laminate strength (g / 15mm width)
(C) It measured about the gas-barrier laminated body which performed the retort process. The gas barrier laminate is formed into a strip shape having a width of 15 mm, and a part of the end thereof is peeled off to a gas barrier film and a sealant film (in the case of the following examples, unstretched polypropylene film), and 100 mm / min by a peeling tester. T-type peeling was performed at a speed of The laminate strength value was determined according to the following criteria.
A: 300 or more B: 100 or more and less than 300 C: less than 100

Examples 1-8 and Comparative Examples 1-6
Water containing resins A to G described below at a compounding ratio shown in Table 1 on the corona-treated surface of a 12 μm thick biaxially stretched polyester film (“H100C” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., PET in Table 1) The medium coating solution was applied and dried to form a coating layer having a thickness of 0.1 μm.
Next, on this polyester film coating layer, silicon monoxide (SiO) was vapor-deposited by a high-frequency heating method using a vacuum vapor deposition apparatus to obtain a gas barrier polyester film having an inorganic thin film thickness of 20 nm.
Next, this gas barrier film was subjected to (i) untreated or (b) printing treatment, and urethane adhesive (Toyo Morton AD-900 and CAT-RT85 10: 1.5 was applied to the inorganic thin film surface or printed surface. And then dried to form an adhesive resin layer having a thickness of 3 μm. An unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film CT P1146” manufactured by Toyobo Co., Ltd.) is formed on the adhesive resin layer surface. In Table 1, CPP) was laminated and subjected to aging treatment at 40 ° C. for 3 days to obtain a gas barrier laminate.
Among them, (b) retort treatment was performed on the gas barrier laminate using the untreated gas barrier film.
About the gas-barrier laminated body obtained by performing various processes, lamination strength, water vapor transmission rate, and oxygen transmission rate were measured and determined. The results are shown in Table 1. In the description of the layer configuration in Table 1, “/” means the main layer configuration, and the description of the relatively thin coating layer on the base film was omitted. “//” means dry lamination, and the description of the adhesive layer is omitted.

Examples 9-10
Nylon 6 having a recycled nylon 6 content of 50% by mass (NY in Table 1) was extruded from a T-die of an extruder at a temperature of 230 ° C. and quenched with a cooling drum to obtain an unstretched nylon sheet having a thickness of 144 μm. . After this unstretched sheet was stretched 3 times in the machine direction at 60 ° C., an aqueous medium coating solution having the compounding ratio shown in Table 1 was applied to one side of the sheet, stretched 3 times in the machine direction at 90 ° C., and 205 ° C. Heat treatment was performed to obtain a biaxially stretched nylon film having a thickness of 16 μm.
A gas barrier film and a gas barrier laminate were obtained in the same manner as in Examples 1 to 8, except that the base film was a biaxially stretched nylon film, and the same measurement was performed for determination. The results are shown in Table 1.

Examples 11 to 15 and Comparative Example 7
In the same manner as in Examples 9 to 10, a gas barrier nylon film was produced, (i) untreated or (b) printed, and the laminate configuration was changed as follows to produce a gas barrier laminate. .
A urethane adhesive (AD-900 and CAT-RT85 manufactured by Toyo Morton) was applied to the corona-treated surface of a 12 μm thick biaxially stretched polyester film (“H100C” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) at a ratio of 10: 1.5. A 3 μm thick adhesive resin layer is formed and laminated with the inorganic thin film surface or printing surface of the gas barrier nylon film on the adhesive resin layer surface, and the gas barrier nylon film is laminated. Got.
An urethane resin adhesive resin layer was formed on the nylon film surface of the obtained gas barrier nylon film in the same manner as described above, and an unstretched polypropylene sheet (made by Toyobo Co., Ltd.) having a thickness of 60 μm was formed on the adhesive resin layer surface. Pyrene film CTP1146 ") was laminated and subjected to an aging treatment at 40 ° C for 3 days to obtain a gas barrier laminate.
This gas barrier laminate was determined by performing the same measurement as described above. The results are shown in Table 1.

(note)
Resin A: As an aqueous polyurethane-based resin aqueous coating, an aqueous polyurethane-based resin aqueous coating obtained by the following method was used. That is, first, a polyester polyol composed of 664 parts by mass of terephthalic acid, 631 parts by mass of isophthalic acid, 472 parts by mass of 1,4-butanediol, and 447 parts by mass of neopentyl glycol was obtained. Next, 321 parts by mass of adipic acid and 268 parts by mass of dimethylolpropionic acid were added to the obtained polyester polyol to obtain a pendant carboxyl group-containing polyester polyol A. Further, 160 parts by mass of hexamethylene diisocyanate was added to 1880 parts by mass of the above polyester polyol A to obtain an aqueous polyurethane resin aqueous coating material.

Resin B: As an aqueous acrylic resin aqueous paint (non-emulsifier type), an aqueous acrylic resin aqueous paint obtained by the following method was used. That is, 40 parts by mass of ethyl acrylate, 30 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, and 10 parts by mass of glycidyl methacrylate were solution-polymerized in ethyl alcohol, and heated while adding water after polymerization to remove ethyl alcohol. did. The aqueous acrylic resin aqueous paint (non-emulsifier type) was obtained by adjusting the pH to 7.5 with aqueous ammonia.

Resin C: “Polyester WR-961” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was used as a water-based polyester resin water-based paint.
Resin D: As the carbodiimide group-containing aqueous resin, “Carbodilite E-02” manufactured by Nisshinbo Co., Ltd. was used.
Resin E: As an oxazoline group-containing aqueous resin, “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd. was used.
Resin F: As an epoxy group-containing aqueous resin, “CAT-2N-206” manufactured by Takamatsu Yushi Co., Ltd. was used.
Resin G: As a melamine group-containing aqueous resin, “Sumimar M50W” manufactured by Sumitomo Chemical Co., Ltd. was used.

The gas barrier film and gas barrier laminate of the present invention maintain gas barrier properties even when subjected to hot water treatment (boil treatment, retort treatment, sterilization treatment), and are suitable for packaging foods, pharmaceuticals and the like.

Claims (23)

In a gas barrier film in which a coating layer is formed on at least one surface of a plastic film and an inorganic thin film is provided on the surface of the coating layer, the coating layer is selected from a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin. At least one selected from water-soluble polyurethane resins, water-dispersible polyurethane resins, water-soluble polyester resins and water-dispersible polyester resins, water-soluble carbodiimide group-containing resins and / or water-dispersible carbodiimide group-containing resins And a gas barrier film characterized by having an oxygen permeability measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH of 10 fmol / m ² / s / Pa or less.   The gas barrier film according to claim 1, wherein the content ratio of the water-soluble polyacrylic resin and / or water-dispersible polyacrylic resin in the coating layer is 10 to 50% by mass based on the resin constituting the coating layer. . The laminate obtained by laminating an unstretched polypropylene film having a thickness of 60 μm on the inorganic thin film had an oxygen permeability of 10 fmol / m ² / s / Pa or less measured under conditions of a temperature of 25 ° C. and a humidity of 80% RH. Te, 120 ° C. relative to the laminate, oxygen permeability ratio after the hydrothermal treatment for 30 minutes (measuring conditions as above) claims, characterized in that is less than 50fmol / m ² / s / Pa Item 3. The gas barrier film according to Item 1 or 2 . The gas barrier film according to any one of claims 1 to 3, wherein the inorganic thin film is formed and then subjected to a heat treatment at 50 ° C or higher. The coating layer is a water-soluble polyurethane resin, a water-dispersible polyurethane resin, a water-soluble polyester resin, and a water-dispersible polyester resin, a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, The gas barrier film according to any one of claims 1 to 4, comprising a carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin. The coating layer comprises a water-soluble polyacrylic resin and / or a water-dispersible polyacrylic resin, a water-soluble polyurethane resin and / or a water-dispersible polyurethane resin, a water-soluble polyester resin and / or a water-dispersible polyester resin, The gas barrier film according to any one of claims 1 to 5, further comprising a water-soluble carbodiimide group-containing resin and / or a water-dispersible carbodiimide group-containing resin. The gas barrier film according to any one of claims 1 to 6 , wherein the inorganic thin film contains silicon oxide. Content of the water-soluble carbodiimide group-containing resin and / or water-dispersible carbodiimide group-containing resin in the coating layer, any one of claims 1 to 7 which is 10 to 50 mass% in the resin criteria constituting the coating layer The gas barrier film according to the description. The gas barrier film according to any one of claims 1 to 8 , wherein the water-soluble polyacrylic resin and / or the water-dispersible polyacrylic resin does not contain an emulsifier. The gas barrier film according to any one of claims 1 to 9 , wherein the plastic film contains one or more plastics selected from polyester, polypropylene, polyamide, polyvinyl alcohol, and ethylene-vinyl acetate copolymer partial hydrolyzate. The gas barrier film according to claim 10 , wherein 10 to 100% by mass of the plastic constituting the plastic film is a recycled plastic. The gas barrier film according to any one of claims 1 to 11 , wherein the coating layer is formed by applying a coating solution to a plastic film and then stretching the coating layer in at least one direction. Gas barrier film of any one of claims 1 to 1 2 in the inorganic thin film surface formed by providing a resin-containing layer. The gas barrier film according to any one of claims 1 to 3 and claims 5 to 13 , wherein the inorganic thin film is formed and then subjected to a heat treatment at 50 ° C or higher. A gas barrier laminate comprising a printed layer formed on the surface of the inorganic thin film of the gas barrier film according to any one of claims 1 to 14 , and a heat seal layer laminated on the surface of the printed layer. . The gas barrier laminate according to claim 15, wherein at least one layer selected from paper and a plastic film is laminated between the printed layer and the heat seal layer. The gas barrier laminate according to claim 15 or 16 , wherein a heat treatment at 50 ° C or higher is performed after the laminate is formed. A gas barrier laminate in which a plastic film is laminated on the inorganic thin film of the gas barrier film according to any one of claims 1 to 14 , wherein the heat treatment at 50 ° C or higher is performed after the plastic film is laminated. Characteristic gas barrier laminate. The gas barrier laminate comprising a plastic film laminated on the inorganic thin film of the gas barrier film according to any one of claims 1 to 14 , wherein the oxygen permeability measured under conditions of a temperature of 25 ° C and a humidity of 80% RH is 10 fmol. / M ² / s / Pa or less, and the oxygen transmission rate after the hydrothermal treatment for 30 minutes at 120 ° C. for the laminate (measurement conditions are the same as above) is 50 fmol / m ² / day / Pa A gas barrier laminate having the following characteristics. The gas barrier laminate according to claim 19 , wherein the laminate is subjected to a heat treatment at 50 ° C or higher after the laminate is formed. The inorganic thin film surface of the gas barrier film of any one of claims 1 to 14, to form a printed layer, in gas-barrier laminate obtained by laminating a heat sealing layer on the surface of the print layer, the temperature 25 ° C., humidity Oxygen permeability measured under conditions of 80% RH is 10 fmol / m ² / s / Pa or less, and oxygen permeability after performing hydrothermal treatment at 120 ° C. for 30 minutes on the laminate ( The gas-barrier laminate is characterized in that the measurement conditions are the same as above) of 50 fmol / m ² / day / Pa or less. The gas barrier laminate according to claim 21, wherein at least one layer selected from paper and a plastic film is laminated between the printed layer and the heat seal layer. 23. The gas barrier laminate according to claim 21 or 22 , wherein a heat treatment at 50 [deg.] C. or higher is performed after the laminate is formed.