JP2005225078A - Gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film having oxygen barrier properties corresponding to those of an aluminum laminated product and solving the problem related to bending fatigue resistance (Gelvo characteristics), transparency and the adhesiveness with a base material. <P>SOLUTION: The gas barrier film is constituted by laminating a resin composition layer, which comprises an acrylic resin containing 50 wt.% or above of N-methylolacrylamide, a water soluble polymer and an inorganic laminar compound, on a thermoplastic resin base material having a thin film, which is composed of aluminum oxide and silicon oxide, formed thereon. Preferably, the water-soluble polymer is polyvinyl alcohol. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention achieves both oxygen barrier properties, bending fatigue resistance (Gelbo properties), adhesion and productivity, and further, under high humidity even after a retort test (treated in hot water at 120 ° C. under pressure for 30 minutes). The present invention relates to a gas barrier film having both oxygen barrier properties and adhesive properties.

  Conventionally, films made of thermoplastic resins such as polyolefin, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polyamide, especially oriented polypropylene, polyethylene terephthalate, polyamide, and other films have excellent mechanical properties, heat resistance, and transparency. Are widely used as packaging materials. However, when these films are used for food packaging, the gas permeability is too large, so that the oxygen barrier property is insufficient, and the contents are easily deteriorated due to oxidative degradation or aerobic microorganisms. Usually, other methods such as laminating other film layers having good oxygen barrier properties are often used.

As the most typical means, a method of laminating a metal foil such as aluminum or depositing the metal on the surface of the thermoplastic resin film is used, and excellent gas barrier properties, particularly oxygen barrier properties are effectively used. It is utilized.
However, these aluminum laminates and vapor-deposited films are opaque, and there is a disadvantage that the contents cannot be visually recognized when food packaging is performed using these. In addition, there is a disadvantage that a metal detector cannot be used for inspection of foreign matter in the contents. Moreover, although the aluminum laminated product has the best gas barrier property, since it cannot be incinerated, it has a waste disposal problem. Moreover, since a large amount of energy is consumed when manufacturing aluminum foil, it has a problem of promoting global warming.

  On the other hand, various transparent plastic film materials having low gas permeability have been conventionally known, for example, films made of polyvinyl alcohol, polyethylene vinyl alcohol, and polyvinylidene chloride resin. However, these films alone are insufficient in physical properties such as strength, elongation, water resistance, heat resistance, etc., compared to oriented polypropylene, polyester, polyamide, and other films, particularly polyvinyl alcohol and polyethylene vinyl. Alcohol and the like have very high hygroscopicity and are difficult to handle because the end face of the roll film becomes petal-like due to moisture absorption, and the target gas barrier property is also greatly reduced by moisture absorption.

  Further, since the level of gas barrier property obtained by these films is still not sufficient as compared with the aluminum laminated film, a highly transparent film having a high gas barrier property is strongly demanded. is the current situation.

  On the other hand, in order to solve these problems, a method of applying a barrier resin such as polyvinyl alcohol, polyethylene vinyl alcohol, or polyvinylidene chloride to oriented polypropylene, polyester, polyamide, or the like has been studied, and in particular, polyvinylidene chloride. Is often used. However, polyvinyl alcohol or polyethylene vinyl alcohol alone has a problem that the peel strength is insufficient. Since polyvinylidene chloride coated film contains chlorine, it has been pointed out that it may pollute the global environment during combustion. Therefore, there is a strong demand for an oxygen gas barrier film made of a material that does not use chlorine, and development is being studied.

  In view of the above circumstances, a film in which an inorganic substance such as silicon oxide (for example, see Patent Document 1) or aluminum oxide (for example, see Patent Document 2) is deposited on the surface of a base material has been developed. These vapor-deposited films do not generate harmful substances due to combustion and have good transparency, but lack the flexibility of the inorganic film, so that there is a problem that cracks tend to occur and the barrier properties are reduced (for example, (See Patent Document 3). Moreover, although the barrier film which consists of a partially neutralized product of polyvinyl alcohol and poly (meth) acrylic acid has been proposed, it requires heat treatment at high temperature, and there is a problem of lowering productivity and film physical properties (for example, , See Patent Document 4). In addition, barrier films formed from acrylic acid and acrylamide resins have been proposed, but these proposals also require heat treatment at high temperatures, resulting in problems such as reduced productivity and film properties, and sufficient oxygen barrier properties. Is not obtained (see, for example, Patent Document 5). In addition, there is a proposal of a barrier film coated with a dispersion composed of charged particles and polyvinyl alcohol. However, since polyvinyl alcohol does not react, retort treatment at a temperature higher than the glass transition temperature of polyvinyl alcohol (hot water at 120 ° C. under pressure) In 30 minutes), the polyvinyl alcohol dissolves, so that there is a problem that it cannot be applied to the retort treatment (see, for example, Patent Document 6).

As a transparent vapor-deposited barrier film, a film mainly composed of aluminum oxide has insufficient oxygen barrier properties and has a problem of bending resistance (for example, see Patent Document 7). In addition, as an example of the A1 ₂ O ₃ .SiO ₂ system as the gas barrier film having retort property, there is one in which A1 ₂ O ₃ and SiO ₂ are sequentially laminated, but the manufacturing apparatus becomes very large. . In addition, these thin film-based gas barrier films are still insufficient in gas barrier properties and flex resistance. That is, in order to have retort resistance, the thickness of the thin film is required to be above a certain level (for example, 2000 mm), but in order to improve the bending resistance, there is a problem that the thinner is better. What is currently used for retort requires attention in its handling (see, for example, Patent Document 8). As described above, a transparent gas barrier film having sufficient oxygen barrier property and retort resistance and high flexibility is not known as compared with an aluminum laminated product.

Japanese Examined Patent Publication No. 53-12953 (Claims) Japanese Patent Laid-Open No. 62-179935 (Claims) Japanese Patent Laid-Open No. 5-179033 (Examples 1 and 2) Japanese Patent Application Laid-Open No. 7-102083 (Example 1) JP 2003-128808 A (Examples 1 to 4) JP-A-9-316236 (Claims) JP 2003-71969 A (Examples 1 and 2) JP-A-2-194944 (Examples 1 to 5)

  The present invention has been made against the background of the problems of the prior art, has oxygen barrier properties comparable to aluminum laminates, and solves the problems of bending fatigue resistance (gelbo characteristics), transparency, and adhesion to the substrate. To do.

  As a result of intensive studies and studies to solve the above problems, the present inventors have finally completed the present invention. The present invention is described in detail below.

(1) Heat in which a thin film made of aluminum oxide and silicon oxide is formed on a resin composition layer made of an acrylic resin containing 50% by weight or more of N-methylolacrylamides, a water-soluble polymer, and an inorganic layered compound A gas barrier film laminated on a plastic substrate.

(2) The gas barrier film according to (1), wherein the water-soluble polymer is polyvinyl alcohol.

(3) The gas barrier film according to (1) or (2), wherein the inorganic layered compound has an average particle size of 3 μm or less and an aspect ratio of 100 to 4000.

(4) The gas barrier film according to any one of (1) to (3), wherein 5 to 50% by weight of an inorganic layered compound is contained in the resin composition layer.

(5) The gas barrier film according to any one of (1) to (4), wherein an acrylic monomer other than N-methylolacrylamides in the acrylic resin is water-soluble.

(6) The gas barrier film according to (5), wherein an acrylic monomer other than N-methylolacrylamides has a hydroxyl group or an amide group.

(7) The gas barrier film according to any one of (1) to (6), wherein the thermoplastic resin base material is any one of polyethylene terephthalate resin, polypropylene resin, and polyamide resin.

(8) The gas barrier film according to any one of (1) to (7), wherein the ratio of aluminum oxide in the thin film is 20 wt% or more and 99 wt% or less, and the film thickness is 50 to 3000 mm.

(9) The gas barrier film according to any one of (1) to (8), wherein the thin film satisfies the following formula.
D = 0.01A + b
(Where D = specific gravity of the thin film, A =% by weight of aluminum oxide in the thin film, 1.6 ≦ b ≦ 2.2)

(10) The gas barrier film according to (1), wherein the resin composition layer has an adhesive layer between the thin films.

(11) The gas barrier film according to any one of (1) to (10), wherein the oxygen permeability measured under conditions of 23 ° C. and 90% relative humidity is 1 cc / m ² · 24 hr · atm or less.

  The film obtained by the present invention provides a gas barrier film excellent in transparency, adhesion to a substrate, transparency, advanced oxygen barrier properties, and gelbo properties. The gas barrier film of the present invention can be suitably used alone or as a laminate with various polymer films and the like as a packaging material for foods, pharmaceuticals, daily goods, and industrial products. Furthermore, the present invention can be suitably used for food applications that require sterilization by retort treatment (treatment in hot water at 120 ° C. under pressure for 30 minutes).

Hereinafter, the present invention will be described in detail.
As a monomer used for the acrylic resin used for the resin composition layer of the present invention, N-methylolacrylamides are used. Moreover, it is also possible to copolymerize the other monomer which has a polymerizable unsaturated double bond as needed. In the present specification and claims, the term “acryl” means acryl in a broad sense, and includes, for example, methacryl.
As the monomer used in the present invention, copolymerization may be performed using (meth) acryl having a hydroxyl group and a polymerizable unsaturated double bond, and (meth) acrylamides and polymerizability may be used as necessary. A carboxylic acid having an unsaturated double bond can also be used in combination.

  Examples of N-methylol acrylamides used in the resin composition layer of the present invention include N-methylol (meth) acrylamide, N, N-dimethylol acrylamide, alkyl etherified N-methylol (meth) acrylamide, and the like. -It is preferable to use methylol acrylamide, and it is preferable that 50 weight% or more is contained when the whole acrylic resin is 100 weight%. More preferably, it is contained in an amount of 70% by weight or more, and more preferably 90% by weight or more. The upper limit is not particularly limited and may be 100% by weight.

  In addition to N-methylolacrylamides, a (meth) acrylic monomer having a hydroxyl group and a polymerizable unsaturated double bond can be copolymerized as necessary. Examples of the (meth) acryl having a hydroxyl group and a polymerizable unsaturated double bond include 2-hydroxyethyl (meth) acrylate and 2-hydroxyalkyl (meth) acrylate.

  Other acrylamides that can be copolymerized include amide groups such as acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide, etc. Monomer.

  Moreover, you may copolymerize the monomer which has another polymerizable unsaturated double bond. For example, as carboxylic acid having a polymerizable unsaturated double bond, for example, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride And unsaturated fatty acids.

  Furthermore, as other monomers, for example, alkyl (meth) acrylate, glycerin (meth) acrylate, polyethylene glycol mono (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, epoxy (meth) acrylate, vinylpyrrolidone, (meth ) Acrylamide styrene, vinyl toluene, methyl styrene, allyl alcohol, alkyl vinyl ether, ethylene, propylene, butadiene, isoprene, α-olefin, acrylonitrile and the like.

  These monomers that can be copolymerized are preferably water-soluble from the viewpoint of versatility in the production process.

  The acrylic resin used for the resin composition layer of the present invention is produced, for example, in water / solvent, in the presence of the monomer and initiator, in an inert gas stream, preferably at 40 to 95 ° C. for 1 to 24 hours. Done. The solvent is preferably water-soluble, such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, ethylene glycol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, diethylene glycol, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, triethylene glycol, Examples include triethylene glycol monoalkyl ether, triethylene glycol dialkyl ether, propylene glycol, glycerin and the like. Among these, a water / alcohol system is preferable from the viewpoint of drying and versatility, and isopropyl alcohol is particularly preferable. A solvent may be used independently and may use 2 or more types together.

  The initiator is preferably a water-soluble radical initiator and is not particularly limited. Examples of the polymerization initiator in the polymerization step include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, hydrogen peroxide, azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, An azo initiator such as a cyclic azoamidine compound such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride and an azonitrile compound such as 2-carbamoylazoisobutyronitrile is used. . At this time, alkali metal sulfites such as sodium hydrogen sulfite, metabisulphite, sodium hypophosphite, Fe (II) salt such as molle salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiourea , L-ascorbic acid (salt), erythorbic acid (salt) and other accelerators may be used in combination. The radical initiator may be mixed and dissolved from the beginning in the reaction system at room temperature, or may be dropped into the reaction system over several hours.

  The water-soluble polymer used in the resin composition layer of the present invention is preferably a polymer that can be completely dissolved or finely dispersed in water at room temperature, for example, cellulose such as polyvinyl alcohol and derivatives thereof, carboxymethyl cellulose, and hydroxyethyl cellulose. Derivatives, starches such as oxidized starch, etherified starch, dextrin, copolymer polyesters containing polar groups such as polyvinylpyrrolidone and sulfoisophthalic acid, vinyl polymers such as polyhydroxyethyl methacrylate and its copolymers, acrylic Examples include polymers, urethane polymers, ether polymers, and functional group-modified polymers such as carboxyl groups and amino groups of these various polymers. Among these, it is preferable that at least one kind is a polyvinyl alcohol polymer and a derivative thereof, particularly preferably polyvinyl alcohol having a saponification degree of 75 mol% or more, polyvinyl alcohol in which 40 mol% or less of all hydroxyl groups are acetalized, It is a copolymerized polyvinyl alcohol having a vinyl alcohol unit of 60 mol% or more. 100-5000 are preferable and, as for the polymerization degree of polyvinyl alcohol and its derivative (s), 200-3000 are more preferable.

  The inorganic layered compound used in the resin composition layer of the present invention is an inorganic compound in which ultrathin unit crystal layers overlap to form one layered particle, and those that swell and cleave in a solvent are preferable. Among these, a clay compound having swelling property to a solvent is particularly preferably used. The clay compound having swellability to the solvent in the present invention may be natural or synthesized. Typical examples include kaolinite, halloysite, montmorillonite, verculite, dickite, nacrite, antigolite, pyrophyllite, hectorite, beidellite, margarite, talc, tetrasilic mica, muscovite, phlogopite. Chlorite and the like.

  As the inorganic layered compound, those having an average particle size of 3 μm or less and an aspect ratio of 100 to 4000 are preferably used from the viewpoint of gas barrier property, cost, and the like. From the viewpoint of gas barrier properties, this aspect ratio is preferably 100 or more, more preferably 200 or more, and particularly preferably 500 or more. Obtaining an inorganic layered compound having an aspect ratio exceeding 4000 is technically difficult and expensive. In terms of manufacturability, the aspect ratio of 2000 or less is easily available, and 1500 or less is more easily available. From the viewpoint of the balance between gas barrier properties and manufacturability, the aspect ratio is preferably in the range of 200 to 3000. The method of measuring the aspect ratio is the average of the 50% average particle diameter (L) using a laser diffraction particle size distribution analyzer (LMS-30; manufactured by Seishin Enterprise) and the average thickness (a) of the interplanar spacing using a transmission electron microscope. The aspect ratio (X) can be determined as X = L / a.

  The average particle size of the inorganic stratiform compound is preferably 3 μm or less in terms of film forming property or moldability. Here, as the measurement method, a 50% median diameter of a laser diffraction particle size distribution meter (LMS-30, manufactured by Seishin Enterprise Co., Ltd.) can be obtained, and an average particle diameter can be obtained. From the viewpoint of transparency, the particle size is more preferably 2 μm or less. When used for applications where transparency is important (for example, food packaging applications), the particle size is particularly preferably 1 μm or less. Although a minimum is not specifically limited, 0.01 micrometer or more is preferable from a gas-barrier viewpoint.

  The inorganic layered compound of the resin composition layer of the present invention is preferably contained in an amount of 5 to 50% by weight in the resin composition layer. If it is 5% by weight or less, sufficient barrier properties may not be obtained. If it is 50% by weight or more, there is a risk of causing cohesive failure of the barrier layer in the peel test. The inorganic layered compound is preferably 7 to 45% by weight, more preferably 10 to 40% by weight in the resin composition layer.

  N-methylol capable of generating a chemical bond with the hydroxyl group of the water-soluble polymer in addition to the water-soluble polymer in improving the durability of the gas barrier film coating film of the present invention and the adhesion to the substrate. It is preferable to apply, dry, and heat-treat a coating solution obtained by mixing an inorganic layered compound with a polymer mixed solution obtained by mixing an acrylic resin having a group. It is also possible to separately extrude and laminate a resin composition, or to prepare a separate film and laminate it by a method such as dry lamination using an adhesive. And most preferred. The blending ratio is preferably in the range of 10 to 90% by weight of the solid content of the acrylic resin solution and 90 to 10% by weight of the solid content of the water-soluble polymer, more preferably 20% of the solid content of the acrylic resin solution. It is desirable that the solid content of ˜80 parts by weight and the water-soluble polymer is in the range of 80˜20% by weight, and the inorganic layered compound is contained in the dried coating film in an amount of 5˜50% by weight, preferably 7˜45. % By weight, more preferably 10 to 40% by weight.

  The thickness of the resin composition layer in the present invention is preferably at least 0.2 μm in order for the film to exhibit sufficient gas barrier properties. Preferably it is 0.7 micrometer or more. The upper limit is not particularly limited, but is preferably less than 10 μm from the viewpoint of adhesion and bending fatigue resistance. Moreover, it is preferable that the polymer concentration in the coating agent used for manufacture is in the range of 5 to 50% by weight of the entire solution. If the solution is too dilute, it will be difficult to coat a layer having a thickness necessary for exhibiting sufficient gas barrier properties, and a large amount of heat will be required to evaporate water and the solvent in the coating film forming process by heating. Prone to problems. On the other hand, when the concentration of the solution is too high, the solution viscosity becomes too high, and there is a possibility that a problem that causes deterioration in operability during mixing or coating may occur.

  In the coating agent used in the present invention, it is preferable that 0.01 to 5 parts by weight of a wettability improver is mixed with 100 parts by weight of resin solids. By mixing the wettability improving agent, the coating property to the thermoplastic resin film is improved, and a film with few coating defects can be obtained. When the mixing amount of the wettability improving agent is less than 0.01 part by weight, the wettability to the thermoplastic resin film is insufficient, and a film having many coating defects may be obtained. On the other hand, when the mixing amount of the wettability improving agent exceeds 5 parts by weight, the peeling strength may be deteriorated.

  As such a wettability improver, any surfactant that can reduce the surface tension of an aqueous solution of a water-soluble polymer or a polyvinyl alcohol-based resin may be used, and various surfactants, water-soluble solvents, aqueous resins, and the like can be used. .

  Examples of various surfactants include higher alcohol sulfates, higher alkyl ether sulfates, sulfates such as sulfated oils, sulfated fatty acid esters, sulfated olefins, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. Carboxylates such as sulfonate, phosphate, soap, higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide Additives, oil / fat ethylene oxide adducts, polypropylene glycol ethylene oxide adducts and other polyethylene glycol type nonionic surfactants, fatty acid esters of glycerol, pentaerythritol fats Polyhydric alcohol type nonionic surfactants such as acid esters, fatty acid esters of sorbitol, fatty acid esters of sorbitan, fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines, amino salts and quaternary Examples include ammonium salt type cationic surfactants, amino acid type, betaine type, sulfate ester type, sulfonate type, and phosphate ester type amphoteric surfactants.

  As the water-soluble solvent, various solvents can be used as long as there is no problem in miscibility with an aqueous polyvinyl alcohol resin solution. For example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, ethylene Glycol monobutyl ether, glycerin and the like can be used.

  The film of the present invention exhibits good oxygen gas barrier properties under high humidity by heat treatment. In order to exhibit sufficient oxygen gas barrier properties and sufficient water resistance under high humidity, the film is preferably heat-treated at a temperature of 110 ° C. or higher. Furthermore, it is more preferable to perform heat treatment at 120 ° C. or higher, and it is particularly preferable to perform heat treatment at 135 ° C. or higher and 170 ° C. or lower. If the temperature of the heat treatment is too low compared to the above conditions, sufficient oxygen gas barrier properties and adhesiveness may not be obtained. Further, when heat treatment is performed at a high temperature of 170 ° C. or higher, there may be a problem that film physical properties are deteriorated. The drying time is 15 seconds or longer, preferably 40 seconds or longer. The upper limit is 10 minutes or less, preferably 8 minutes or less.

When applying the above coating agent and drying and heat-treating, it is considered that the methylol group of the acrylic resin exhibits excellent bending fatigue resistance and adhesion by condensation reaction with the hydroxyl group of the water-soluble polymer, etc. It is done. Whether or not the condensation reaction is proceeding can be judged by carrying out a water immersion test of the coating film. In addition, since the barrier layer contains an inorganic layered compound that swells and cleaves in water or a solvent, the permeation path of oxygen molecules is substantially increased, so that the barrier layer can have sufficient barrier properties.
In addition, the gas barrier film of the present invention provides a heat-resistant barrier layer by condensation reaction of the methylol group of the acrylic resin with the hydroxyl group of the water-soluble polymer, so that retort treatment (hot water at 120 ° C. under pressure) It is possible to provide a gas barrier film that maintains oxygen barrier properties and adhesiveness under high humidity even after treatment for 30 minutes.

In the gas barrier film of the present invention, a thermoplastic base material in which an inorganic thin film is formed on a thermoplastic base material is used. As an inorganic thin film, what consists of aluminum oxide and a silicon oxide is preferable. The aluminum oxide referred to herein, Al, A1O, consists of a mixture of A1 various aluminum oxides such as ₂ O _3, the content and the like of each in the aluminum oxide differs create conditions. Silicon oxide is considered to be composed of Si, SiO, SiO ₂ or the like, and the ratio of these also varies depending on the preparation conditions. In the present invention, the ratio of aluminum oxide in the thin film is desirably 20% by weight or more and 99% by weight or less, and preferably 30% by weight or more and 95% by weight or less. Further, this component may contain a trace amount (up to 3% with respect to all components) of other components within a range where the characteristics are not impaired. The thickness of the thin film is not particularly limited, but is preferably 50 to 2000 mm, more preferably 70 to 1000 mm from the viewpoint of gas barrier properties and flexibility. For the production of such an aluminum oxide / silicon oxide thin film, a vacuum deposition method, a sputtering method, a PVD method (physical vapor deposition method) such as ion plating, a CVD method (chemical vapor deposition method), or the like is appropriately used. For example, in the vacuum evaporation method, a mixture of A1 ₂ O ₃ and SiO ₂ or A1 and SiO ₂ is used as an evaporation source material, and resistance heating, high frequency induction heating, electron beam heating, etc. are used as a heating method. Can be used. Moreover, you may use reactive vapor deposition which introduce | transduced oxygen, nitrogen, water vapor | steam etc. as reactive gas, or used means, such as ozone addition and ion assist. Further, the creation conditions may be changed as long as the object of the present invention is not impaired, such as applying a bias to the substrate, raising the substrate temperature, or cooling the substrate. The same applies to other production methods such as the sputtering method and the CVD method.

  In the present invention, the specific gravity of an inorganic vapor-deposited thin film refers to the ratio of the mass of a substance occupying a certain volume at a certain temperature to the mass of a standard substance having the same volume (water at 4 ° C.). The specific gravity is usually measured by measuring the mass and volume of an object and determining the ratio of the same volume of water at 4 ° C., but it is difficult to measure the volume in the measurement of the thin film of the present invention. Therefore, it is desirable to use a specific gravity measurement method as described in (JIS K7112) after first removing the thin film from the substrate or by dissolving only the substrate to form a single film consisting of only the thin film. . For example, in the float / sink method, the sample can be immersed in a solution having a known specific gravity, and the specific gravity of the thin film can be measured from the float / sink state. As this solution, a mixed solution of carbon tetrachloride and bromoform or methylene iodide can be used. The specific gravity value can also be measured by a density gradient tube method in which a single film is immersed in a solution having a continuous density gradient.

  The specific gravity value of the thin film thus obtained is related to the weight% of aluminum oxide in the thin film by D = 0.01A + b (D: specific gravity of the thin film, A: weight% of aluminum oxide in the thin film) ), In the region where the value of b is smaller than 1.6, the structure of the aluminum oxide / silicon oxide thin film becomes rough and sufficient gas barrier properties may not be obtained. In addition, when the specific gravity value of the thin film is in the region where the b value is larger than 2.2, the initial gas barrier property after film formation is excellent, but the film becomes too hard, and the mechanical properties, particularly the gelbo properties are high. Inferior, the decrease in gas barrier properties after treatment increases, and it may be difficult to use as a gas barrier film. For the above reasons, the specific gravity of an aluminum oxide / silicon oxide thin film preferable as a gas barrier film is the relationship between the specific gravity of the thin film and the composition ratio of aluminum oxide in the thin film: D = 0.01A + b (D: specific gravity of the thin film, A: thin film) When expressed by the relational expression of (weight% of aluminum oxide in the inside), the value of b is 1.6 to 2.2, and more preferably 1.7 to 2.1.

  As long as the gas barrier film of the present invention includes three layers of the resin composition layer, the inorganic thin film layer, and the thermoplastic resin base material layer, other layers may be laminated. Further, the stacking order is not limited. In other words, the resin composition layer may be laminated on the inorganic thin film layer, or the resin composition layer may be laminated on the bottom. However, the lamination on the inorganic thin film layer improves the durability (gelbo characteristics) of the entire film. Is preferable.

  In the present invention, as the thermoplastic resin base material when the gas barrier layer is laminated, a film made of polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, nylon 6, nylon 66, nylon Examples thereof include a film made of polyamide resin such as 46, and a film made of polyolefin resin such as polyethylene and polypropylene. The film which consists of a mixture of the said resin, or those laminated bodies may be sufficient. Of these, any one of polyethylene terephthalate, polypropylene, and polyamide resin is preferable. In addition, the surface of the thermoplastic resin substrate may be subjected to physical treatment such as corona treatment and chemical treatment such as coupling agent treatment in order to improve adhesion. Moreover, you may use what coated the easily bonding layer.

  When producing the gas barrier film of the present invention, an adhesive layer may be provided on the inorganic vapor-deposited thin film. In other words, the primer layer comprising a polyester or polyurethane resin and polyisocyanate may be laminated, and the coating solution may be applied, followed by heat treatment. The primer layer has an effect of further improving the adhesion between the inorganic vapor-deposited thin film layer of the present invention and the gas barrier resin composition layer.

  Examples of the polyester that forms the primer layer include polyester polyols obtained by reacting polyvalent carboxylic acids or their dialkyl esters or mixtures thereof with glycols or mixtures thereof. As the polyurethane, polyester or polyol, and in some cases, a bifunctional glycol obtained by chain extension with a bifunctional isocyanate can be suitably used.

  These polyesters or polyurethanes preferably have a glass transition temperature of −50 to 100 ° C., more preferably −40 to 90 ° C., and still more preferably −20 to 80 ° C. The weight average molecular weight of these polyesters or polyurethanes is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, still more preferably from 10,000 to 40,000.

  Examples of the polyisocyanate forming the primer layer include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4. '-Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro- 4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. Polyisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate And aliphatic polyisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate.

  Containing a terminal isocyanate group obtained by a reaction with a polyfunctional polyisocyanate compound such as isocyanurate, burette, or allophanate derived from the polyisocyanate monomer, or a trifunctional or higher functional polyol compound such as trimethylolpropane or glycerin; A polyfunctional polyisocyanate compound or the like can also be used.

  In the gas barrier film of the present invention, a heat-sealable resin layer called a sealant may be formed on the resin layer made of the coating agent. The heat-sealable resin layer is usually formed by an extrusion lamination method or a dry lamination method.

  The thermoplastic polymer for forming the heat-sealable resin layer is not particularly limited as long as the sealant adhesiveness can be sufficiently expressed. Polyethylene resins such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polypropylene Resin, ethylene-vinyl acetate copolymer, ethylene-α-olefin random copolymer, ionomer resin and the like can be used. Usually, heat-sealable resins that are not chlorine-containing resins are preferred from the viewpoint of environmental problems during incineration.

The resin composition layer in the gas barrier film of the present invention preferably has an oxygen permeability of 1 cc / m ² · 24 hr · atm or less measured at 23 ° C. and 90% relative humidity. More preferably, it is 0.7 cc / m ² · 24 hr · atm or less, and most preferably 0.5 cc / m ² · 24 hr · atm or less. If it exceeds 1 cc / m ² · 24 hr · atm, the intended gas barrier effect may not be obtained. The oxygen permeability referred to here is a 10 cm × 10 cm sample set in a measuring instrument using an OX-TRAN 10 / 50A manufactured by MODERN CONTROLS INC, and a flow of oxygen gas (total flow rate 100 cc / min, each cell The flow rate is 10 cc / min), which is a value measured at a measurement time of 8 hours.

The gas barrier layer in the gas barrier film has an oxygen permeability of 1 cc measured under conditions of 23 ° C. and 90% relative humidity after the retort treatment (treatment in hot water at 120 ° C. under pressure for 30 minutes). / M ² · 24 hr · atm or less is preferable. More preferably, it is 0.7 cc / m ² · 24 hr · atm or less, and most preferably 0.5 cc / m ² · 24 hr · atm or less.

  The gas barrier film preferably has a laminate strength of 0.2 kgf / 15 mm or more before and after retort treatment (treatment in hot water at 120 ° C. under pressure for 30 minutes). More preferably, it is 0.25 gf / 15 mm or more, and most preferably 0.3 kgf / 15 mm or more.

  The film of the present invention and the laminated film using the same can be applied to various fields that require high oxygen gas barrier properties. The gas barrier film of the present invention can be used alone or laminated with various polymer films. As a body, it is suitable for the field of food, pharmaceuticals, daily goods, and packaging materials for industrial products. Moreover, when using it for the packaging use of a foodstuff and a pharmaceutical as an advanced gas barrier film, it can be used as a molded article by laminating printing or other films on the film of the present invention.

  When using the film of this invention as a laminated body, when a base material is a transparent material, it is preferable to have transparency. This transparency is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more in terms of the total light transmittance at a wavelength of 500 nm. Such transparency can be suitably measured with, for example, a commercially available spectrophotometer (manufactured by Hitachi, Ltd., self-recording spectrophotometer type 330). Further, the haze (HAZE) is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less, and a commercially available haze meter (manufactured by Suga Test Instruments, etc.) is used for the measurement.

  According to the present invention, it is possible to provide a film that is excellent in high oxygen gas barrier property and sealant adhesiveness under high humidity and is effective for environmental protection, which has been a problem in recent years.

  Next, the present invention will be specifically described using the following examples and comparative examples, but the present invention is not limited thereto. The characteristic value was evaluated by the following method. In the examples and comparative examples, “parts” means “parts by weight”.

The oxygen permeability was measured by setting a 10 cm × 10 cm sample in a measuring instrument using OX-TRAN 10 / 50A manufactured by MODERN CONTROLS INC, and flowing oxygen gas under conditions of 23 ° C. and 90% relative humidity (total The flow rate was 100 cc / min, the flow rate of each cell was 10 cc / min), and the measurement time was 8 hours. The oxygen permeability (P ₁ ) of the gas barrier film coating layer and the inorganic thin film layer was determined by the following calculation formula.
1 / P _t = 1 / P ₁ + 1 / P ₂
However,
P _t : Oxygen permeability P _{2 of a} laminated film composed of a coating (resin composition) layer, an inorganic thin film layer, a base film layer and a laminate film layer P ₁ : Oxygen permeability P ₂ composed of a coating layer and an inorganic thin film layer : Oxygen permeability composed of base film layer and laminate film layer The unit of oxygen permeability was indicated by cc / m ² · 24 hr · atm.

Lamination strength is obtained after 3 g / m ² of a polyether polyurethane adhesive (trade name: Ad Coat, manufactured by Toyo Morton Co., Ltd.) is applied as a laminating adhesive to a film obtained by applying a coating solution to a thermoplastic substrate and drying it. The laminated polypropylene film (thickness 40 μm, manufactured by Toyobo Co., Ltd .: P1128) was bonded to the corona discharge treated surface and aged at 40 ° C. for 72 hours to obtain a laminate film. The laminate film (15 mm width) was measured between the laminate adhesive layer and the barrier coat layer using a tensile tester UTM2 (manufactured by Toyo Keiki Co., Ltd.) at a peeling rate of 10 cm / min at 23 ° C. and a relative humidity of 65%. Degree of strength when peeled.

  The test method for bending fatigue resistance (hereinafter referred to as gelbo characteristics) was evaluated using a so-called gelboflex tester (manufactured by Rigaku Corporation). As a condition, a sample piece of 112 inch × 8 inch in (MIL-B131H) is made into a cylindrical shape with a diameter of 3 inch, and a twist of 400 degrees is added at a stroke of 3 inch. The results of oxygen permeability were shown. The oxygen permeability was measured by the method described above.

  The oxygen permeability after the retort treatment was treated with hot water at 120 ° C. under pressure for 30 minutes using TOMY ES-3151, then cooled, taken out of the sample, and dried at 80 ° C. for 2 hours. Measured by the same method as described above.

  The laminate strength after the retort treatment was processed for 30 minutes in hot water at 120 ° C. under pressure using ES-3151 manufactured by TOMY, then cooled, taken out of the sample, dried at 80 ° C. for 2 hours, Measurement was performed by the same method as described above.

  The specific gravity of the inorganic vapor-deposited film was measured by a flotation method after dissolving the PET film.

  The film thickness was measured using a fluorescent X-ray analyzer (Rigaku Denki System 3270). X-rays were generated using a rhodium tube at 50 KV and 50 mA.

A production example of the barrier resin composition layer is shown below.
[Production Example 1]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion-exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 150 parts were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 2.98 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained.

[Production Example 2]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion-exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 120 parts and 30 parts of 2-hydroxyethyl acrylate were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 1.28 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained.

[Production Example 3]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion-exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 120 parts and 30 parts of 2-hydroxyethyl methacrylate were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 4.34 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained.

[Production Example 4]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion-exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 195 parts and 55 parts of 2-hydroxyethyl acrylate were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 1.3 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained.

[Production Example 5]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 120 parts and 30 parts of acrylamide were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 2.86 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained.

[Production Example 6]
As a water-soluble polymer, a separable four-necked flask is equipped with a temperature control regulator, a condenser tube, and a stirring device, charged with 90 parts of ion-exchanged water, and stirred at room temperature, polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA105) 10 parts were added, dissolved at 98 ° C. for 2 hours, cooled to room temperature, filtered and taken out.

[Production Example 7]
As a water-soluble polymer, a separable four-necked flask is equipped with a temperature control regulator, a cooling tube, and a stirring device, charged with 92.5 parts of ion-exchanged water, and stirred at room temperature, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: 7.5 parts of PVA117) was added, dissolved at 98 ° C. for 2 hours, cooled to room temperature, filtered and taken out.

[Production Example 8]
The inorganic layered compound dispersion was manufactured by attaching a temperature control regulator, a condenser, and a stirrer to a separable four-necked flask. , 3 parts of particle diameter 100-2000 nm, average aspect ratio 320) were charged, dispersed with stirring at 80 ° C. for 4 hours, cooled to room temperature, filtered and taken out.

A production example of an inorganic vapor-deposited thin film is shown below.

[Production Example 9]
As an evaporation source, particulate Al ₂ O ₃ (purity 99.5%) and SiO ₂ (purity 99.9%) having a size of about 3 to 5 mm are used, and a stretched polyethylene terephthalate film ( An aluminum oxide / silicon oxide thin film was formed on a 12 μm-thick Toyobo Co., Ltd. product: E5100). Evaporation materials are not mixed, but the inside of the hearth is divided into two by a carbon plate, and a single electron gun (hereinafter referred to as an EB gun) is used as a heating source to heat each of Al ₂ O ₃ and SiO _{2 in} a time-sharing manner. did. At that time, a 200 mm thick film was formed under the conditions shown in Table 1 for the emission current of the EB gun, the heating ratio to Al ₂ O ₃ and SiO ₂ , the film feed rate, the vacuum pressure during vapor deposition, the specific gravity, the composition and the film thickness. It was. The supply amount of oxygen gas was 130 CCM. The cooling temperature of the chill roll was -10 ° C.

[Production Examples 10-15]
As an evaporation source, particulate Al ₂ O ₃ (purity 99.5%) and SiO ₂ (purity 99.9%) having a size of about 3 to 5 mm are used, and a stretched polyethylene terephthalate film ( An aluminum oxide / silicon oxide thin film was formed on a 12 μm-thick Toyobo Co., Ltd. product: E5100). Evaporation materials are not mixed, but the inside of the hearth is divided into two by a carbon plate, and a single electron gun (hereinafter referred to as an EB gun) is used as a heating source to heat each of Al ₂ O ₃ and SiO _{2 in} a time-sharing manner. did. At that time, the emission current of the EB gun was changed from 0.8 to 5.0 A, the heating ratio to Al ₂ O ₃ and SiO ₂ was changed from 10:10 to 50: 1, and the composition was changed. The film feed rate was changed from 100 to 300 m / min to form a film having a thickness of 80 to 1000 mm. Also, the vapor pressure is changed from 1 to 10 ^-5 to 2 x 10 ^-3 Torr by changing the supply amount of oxygen gas to 0 to 5000 CCM, and the cooling temperature of the chill roll is also changed from -20 to 70 ° C. It was. Table 1 shows the emission current of the EB gun, the heating ratio to Al ₂ O ₃ and SiO ₂ , the film feed rate, the vacuum pressure during vapor deposition, the specific gravity, the composition, and the film thickness.

[Production Example 16]
A sample was produced and evaluated in the same manner as in Production Example 9 except that a stretched nylon film (thickness 25 μm, manufactured by Toyobo Co., Ltd .: N2100) was used instead of the stretched polyester of Example 1. Table 1 shows the emission current of the EB gun, the heating ratio of Al ₂ O ₃ and SiO ₂ , the film feed rate, the vacuum pressure during vapor deposition, the specific gravity, the composition, and the film thickness.

  Examples of the gas barrier film of the present invention and comparative examples will be described below.

[Example 1]
To the inorganic vapor-deposited film of Production Example 9, 15 parts of a polyester-based resin (trade name: AD-335AE manufactured by Toyo Morton Co., Ltd.) and 1.5 parts of polyisocyanate (trade name: CAT 10 manufactured by Toyo Morton Co., Ltd.) are mixed to form a membrane. Coating and drying were performed so that the thickness became 0.3 μm. 7 parts of the acrylic resin solution polymerized in Production Example 1, 120 parts of the aqueous polyvinyl alcohol solution dissolved in Production Example 6 and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 were mixed at room temperature, and the paint shaker (TOYOSEIKI Co., Ltd.) was mixed. Manufactured by PAINT SHAKER) for 2 hours. 0.2 parts of polyalkylene glycol-based surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Neugen 110) was mixed with the obtained inorganic layered compound mixture, applied using a 100 μm gap applicator, and dried with hot air And dried at 75 ° C. for 2 minutes. Next, heat treatment was performed at 140 ° C. for 2 minutes with a hot air dryer. The resin coating thickness was 2.2 μm. Next, 100 parts of a polyester-based resin (product name: AD590, manufactured by Toyo Morton Co., Ltd.) and 16 parts of polyisocyanate (product name: CAT-56 manufactured by Toyo Morton Co., Ltd.) are used as a laminating adhesive on the coated surface side of the film. After mixing, coating and drying to a film thickness of 3 μm, pasting with a corona discharge treated surface of an unstretched polypropylene film (thickness 40 μm, manufactured by Toyobo Co., Ltd .: P1128), aging was performed at 40 ° C. for 72 hours. A laminated film was obtained. The laminate film was evaluated for oxygen permeability, oxygen permeability after gelbo test, and laminate strength. The obtained film characteristics are shown in Table 2.

[Example 2]
Using the inorganic vapor deposition film of Production Example 9, a mixture of 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the aqueous polyvinyl alcohol solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 3
Using the inorganic vapor-deposited film of Production Example 9, 43 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 4
Using the inorganic vapor-deposited film of Production Example 9, 43 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was manufactured and evaluated in the same manner as in Example 1 except that the coating was applied by using bar coater # 6. The resin coating thickness was 1.3 μm. The obtained film characteristics are shown in Table 2.

Example 5
Using the inorganic vapor deposition film of Production Example 9, 43 parts of the acrylic resin solution polymerized in Production Example 1, 43 parts of the acrylic resin solution polymerized in Production Example 1 of Production Example 6, and 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6 A sample was produced in the same manner as in Example 1, except that a heat treatment was performed at 160 ° C. for 1 minute using a mixed liquid of 200 parts of the inorganic layered compound dispersion dispersed in Production Example 8. Evaluation was performed. The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 6
Using the inorganic vapor deposition film of Production Example 9, a mixture of 60 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 7, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.7 μm. The obtained film characteristics are shown in Table 2.

Example 7
Using the inorganic vapor deposition film of Production Example 9, a mixed solution of 33 parts of the acrylic resin solution polymerized in Production Example 1, 267 parts of the polyvinyl alcohol aqueous solution of Production Example 7, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.5 μm. The obtained film characteristics are shown in Table 2.

Example 8
Using the inorganic vapor deposition film of Production Example 9, a mixed solution of 43 parts of an acrylic resin solution polymerized in Production Example 3, 257 parts of an aqueous polyvinyl alcohol solution of Production Example 6, and 200 parts of a dispersion of an inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.5 μm. The obtained film characteristics are shown in Table 2.

Example 9
Using the inorganic vapor deposition film of Production Example 9, a mixed solution of 43 parts of an acrylic resin solution polymerized in Production Example 4, 257 parts of a polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of a dispersion of an inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.7 μm. The obtained film characteristics are shown in Table 2.

Example 10
Using the inorganic vapor deposition film of Production Example 9, a mixed solution of 43 parts of an acrylic resin solution polymerized in Production Example 2, 257 parts of an aqueous polyvinyl alcohol solution of Production Example 6, and 200 parts of a dispersion of an inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.5 μm. The obtained film characteristics are shown in Table 2.

Example 11
Using the inorganic vapor deposition film of Production Example 10, a mixture of 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 12
Using the inorganic vapor deposition film of Production Example 11, a mixture of 14 parts of an acrylic resin solution polymerized in Production Example 1, 257 parts of a polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of a dispersion of an inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 13
Using the inorganic vapor deposition film of Production Example 12, a mixed solution of 14 parts of an acrylic resin solution polymerized in Production Example 1, 257 parts of a polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of a dispersion of an inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 14
Using the inorganic vapor-deposited film of Production Example 13, a mixture of 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6 and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 15
Using the inorganic vapor deposition film of Production Example 14, a mixture of 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the aqueous polyvinyl alcohol solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 16
Using the inorganic vapor-deposited film of Production Example 15, 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

Example 17
Using the inorganic vapor deposition film of Production Example 16, a mixed solution of 14 parts of the acrylic resin solution polymerized in Production Example 1, 257 parts of the polyvinyl alcohol aqueous solution of Production Example 6, and 200 parts of the dispersion of the inorganic layered compound dispersed in Production Example 8 A sample was produced and evaluated in the same manner as in Example 1 except that the coating was performed using The resin coating thickness was 2.6 μm. The obtained film characteristics are shown in Table 2.

[Comparative Example 1]
A separable four-necked flask was equipped with a temperature control regulator, a condenser, and a stirrer. At room temperature, 390 parts of ion-exchanged water and 210 parts of isopropyl alcohol and acrylic monomer were used as N-methylolacrylamide (manufactured by Soken Chemical Co., Ltd., N- MAM) 150 parts were charged and dissolved. Furthermore, 1.5 parts of potassium persulfate, 0.06 part of sodium hydrogen sulfite and 1.5 parts of anhydrous sodium acetate were charged and dissolved. Next, the reaction vessel was purged with nitrogen, heated to 65 ° C. in 30 minutes, and reacted at 65 ° C. for 3 hours. The reaction product was cooled to room temperature, filtered and removed. The acrylic resin solution viscosity was measured at 25 ° C. using a BL viscometer (manufactured by TOKIMEC INK). The solution viscosity was 2.98 dPa · s, and an acrylic resin having a solid content concentration of 20% by weight was obtained. As a water-soluble polymer, a separable four-necked flask is equipped with a temperature control regulator, a cooling tube, and a stirring device, charged with 92.5 parts of ion-exchanged water, and stirred at room temperature, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: 7.5 parts of PVA117) was added, dissolved at 98 ° C. for 2 hours, cooled to room temperature, filtered and taken out. The inorganic layered compound dispersion was prepared by attaching a temperature control regulator, a condenser, and a stirrer to a separable four-necked flask, and 97 parts of ion exchange water and montmorillonite (Kunimine Kogyo Co., Ltd., trade name: Kunipia F, particles) 3 parts of a particle having a diameter of 100 to 2000 nm and an average aspect ratio of 320) were charged, dispersed with stirring at 80 ° C. for 4 hours, cooled to room temperature, filtered and taken out. On the corona-treated surface of a stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Toyobo Co., Ltd .: E5100), 15 parts of polyester resin (trade name: AD-335AE manufactured by Toyo Morton Co., Ltd.) and 1.5 parts of polyisocyanate (as an anchor layer) Toyo Morton Co., Ltd., trade name: CAT10) was mixed, and applied and dried to a film thickness of 0.3 μm. 7 parts of an acrylic resin solution, 120 parts of an aqueous polyvinyl alcohol solution, and 200 parts of a dispersion of an inorganic layered compound were mixed at room temperature, and dispersed for 2 hours with a paint shaker (TOYOSEIKI, PAINT SHAKER). 0.2 parts of a polyalkylene glycol surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Neugen 110) is mixed with the obtained inorganic layered compound mixture, and applied to the anchor surface using a 100 μm gap applicator. And dried at 75 ° C. for 2 minutes with a hot air dryer. Next, heat treatment was performed at 140 ° C. for 2 minutes with a hot air dryer. The resin coating thickness was 2.2 μm. Next, 100 parts of a polyester-based resin (product name: AD590, manufactured by Toyo Morton Co., Ltd.) and 16 parts of polyisocyanate (product name: CAT-56 manufactured by Toyo Morton Co., Ltd.) are used as a laminating adhesive on the coated surface side of the film. After mixing, coating and drying to a film thickness of 3 μm, pasting with a corona discharge treated surface of an unstretched polypropylene film (thickness 40 μm, manufactured by Toyobo Co., Ltd .: P1128), aging was performed at 40 ° C. for 72 hours. A laminated film was obtained. The laminate film was evaluated for oxygen permeability, oxygen permeability after gelbo test, and laminate strength. The obtained film characteristics are shown in Table 3.

[Comparative Example 2]
As an evaporation source, particulate Al ₂ O ₃ (purity 99.5%) and SiO ₂ (purity 99.9%) having a size of about 3 to 5 mm are used, and a stretched polyethylene terephthalate film ( An aluminum oxide / silicon oxide thin film was formed on a 12 μm-thick Toyobo Co., Ltd. product: E5100). Evaporation materials are not mixed, but the inside of the hearth is divided into two by a carbon plate, and a single electron gun (hereinafter referred to as an EB gun) is used as a heating source to heat each of Al ₂ O ₃ and SiO _{2 in} a time-sharing manner. did. At that time, a 200 mm thick deposited film was formed at a film feed rate of 200 m / min with an emission current of 2 A of the EB gun, a heating ratio of 30 parts of Al ₂ O ₃ and 10 parts of SiO ₂ . The composition of the deposited film was 35% Al ₂ O ₃ and 65% SiO ₂ . 100 parts of polyester resin (trade name: AD590, manufactured by Toyo Morton Co., Ltd.) and 16 parts of polyisocyanate (trade name: CAT-56, manufactured by Toyo Morton Co., Ltd.) are mixed as a laminating adhesive so that the film thickness becomes 3 μm. After coating and drying, the film was laminated with a corona discharge-treated surface of an unstretched polypropylene film (thickness 40 μm, manufactured by Toyobo Co., Ltd .: P1128) and aged at 40 ° C. for 72 hours to obtain a laminate film. The laminate film was evaluated for oxygen permeability, oxygen permeability after gelbo test, and laminate strength. The obtained film characteristics are shown in Table 3.

[Comparative Example 3]
On the surface of a stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Toyobo Co., Ltd .: E5100), an aluminum oxide layer having a thickness of 200 mm was formed by a reactive vapor deposition method of aluminum and oxygen gas. 100 parts of polyester resin (trade name: AD590, manufactured by Toyo Morton Co., Ltd.) and 16 parts of polyisocyanate (trade name: CAT-56, manufactured by Toyo Morton Co., Ltd.) are mixed as a laminating adhesive so that the film thickness becomes 3 μm. After coating and drying, the film was laminated with a corona discharge-treated surface of an unstretched polypropylene film (thickness 40 μm, manufactured by Toyobo Co., Ltd .: P1128) and aged at 40 ° C. for 72 hours to obtain a laminate film. The laminate film was evaluated for oxygen permeability, oxygen permeability after gelbo test, and laminate strength. The obtained film characteristics are shown in Table 3.

[Comparative Example 4]
As a coating layer, 250 parts of a 15% by weight aqueous solution of a copolyester resin aqueous dispersion (manufactured by Toyobo Co., Ltd .: trade name: MD1200) and 300 parts of an inorganic layered compound dispersion were mixed. The inorganic layered compound dispersion was prepared by attaching a temperature control regulator, a condenser, and a stirrer to a separable four-necked flask, and 97 parts of ion exchange water and montmorillonite (Kunimine Kogyo Co., Ltd., trade name: Kunipia F, particles) 3 parts of a particle having a diameter of 100 to 2000 nm and an average aspect ratio of 320) were charged, dispersed with stirring at 80 ° C. for 4 hours, cooled to room temperature, filtered and taken out. On the corona-treated surface of a stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Toyobo Co., Ltd .: E5100), 15 parts of polyester resin (trade name: AD-335AE manufactured by Toyo Morton Co., Ltd.) and 1.5 parts of polyisocyanate (as an anchor layer) Toyo Morton Co., Ltd., trade name: CAT10) was mixed, and applied and dried to a film thickness of 0.3 μm.
This was coated with the previous coating material and dried, and a laminate film was obtained in the same manner as in Comparative Example 1. The resin coating thickness was 2.8 μm. The obtained film characteristics are shown in Table 3.

  The film obtained by the present invention provides a film excellent in transparency, adhesion to a substrate, transparency, advanced oxygen barrier properties, and bending fatigue resistance (gelbo characteristics). The gas barrier film of the present invention can be suitably used alone or as a laminate with various polymer films and the like as a packaging material for foods, pharmaceuticals, daily goods, and industrial products.

Claims (11)

  A thermoplastic base material in which a thin film made of aluminum oxide and silicon oxide is formed from a resin composition layer made of an acrylic resin containing 50% by weight or more of N-methylolacrylamides, a water-soluble polymer, and an inorganic layered compound Gas barrier film laminated on top.   The gas barrier film according to claim 1, wherein the water-soluble polymer is polyvinyl alcohol.   The gas barrier film according to claim 1 or 2, wherein the inorganic layered compound has an average particle size of 3 µm or less and an aspect ratio of 100 or more and 4000 or less.   The gas barrier film according to any one of claims 1 to 3, wherein the resin layer contains 5 to 50% by weight of an inorganic stratiform compound.   The gas barrier film according to any one of claims 1 to 4, wherein an acrylic monomer other than N-methylolacrylamides in the acrylic resin is water-soluble.   6. The gas barrier film according to claim 5, wherein the acrylic monomer other than N-methylolacrylamides has a hydroxyl group or an amide group.   The gas barrier film according to any one of claims 1 to 6, wherein the thermoplastic resin base material is any one of polyethylene terephthalate resin, polypropylene resin, and polyamide resin.   The gas barrier film according to any one of claims 1 to 7, wherein the ratio of aluminum oxide in the thin film is 20 wt% or more and 99 wt% or less, and the film thickness thereof is 50 to 3000 mm. The gas barrier film according to any one of claims 1 to 8, wherein the thin film satisfies the following formula.
D = 0.01A + b
(Where D = specific gravity of the thin film, A =% by weight of aluminum oxide in the thin film, 1.6 ≦ b ≦ 2.2)   The gas barrier film according to claim 1, wherein the resin composition layer has an adhesive layer between the thin films. The gas barrier film according to any one of claims 1 to 10, wherein the oxygen permeability measured under conditions of 23 ° C and 90% relative humidity is 1 cc / m ² · 24 hr · atm or less.