JP3351208B2 - Gas barrier film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film, and more particularly to a gas barrier film having high gas barrier properties under high humidity and excellent adhesion to a substrate.

[0002]

2. Description of the Related Art In the field of packaging of foods and medicines, if there is intrusion of oxygen or the like from the outside air, the contents cannot be stored for a long period of time due to deterioration of the contents. Is being developed.

[0003] Polymer Engineering and
According to Science, Vol. 20, No. 22, pp. 1543-1546 (December 1986), polyvinylidene chloride, polyvinylidene chloride,
Examples include polyacrylonitrile and polyvinyl alcohol. However, since polyvinylidene chloride contains a chlorine atom and polyacrylonitrile contains a -CN group, environmental problems at the time of disposal have been raised in recent years. Further, since polyvinyl alcohol contains an -OH group, the humidity dependence of gas barrier properties is large, and the gas barrier properties are significantly reduced at high humidity. Even with ethylene-vinyl alcohol copolymers having improved humidity dependence of polyvinyl alcohol, the gas barrier properties at high humidity are not yet satisfactory.

On the other hand, silicon oxide (JP-B-53-12953)
And aluminum oxide (JP-A-62-1799).
No. 35, etc.) have been developed. However, the formation of these films requires a very high cost due to the addition of a vapor deposition process, the lack of flexibility of the inorganic coating, poor adhesion to the substrate, etc. There is a problem.

As a means for solving these problems, a film (for example, Japanese Patent Application Laid-Open No. 56-4563) in which a coating made of a metal oxide and polyvinyl alcohol is provided on a substrate has been developed. However, the gas barrier properties of these are not yet at a satisfactory level. Further, a film having a gas barrier layer composed of an inorganic layered compound and a highly hydrogen-bonding compound (JP-A-6-93133, JP-A-7-41)
685, etc.), however, in order to obtain a high barrier property, a long time drying or heat treatment is required in the process of forming the gas barrier layer. Is also low. If the adhesion to the base material is low, when processed into a packaging bag or the like, the package will be broken or the bag will be deformed, so that a highly reliable packaging material cannot be obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional gas barrier film, and to provide a gas barrier having a high gas barrier property even under high humidity and a high adhesion to a substrate. Is to provide a film.

[0007]

According to the present invention, in order to achieve the above-mentioned object, a water-soluble polymer A and a water-soluble or water-dispersible polyester are provided on at least one surface of a thermoplastic resin base film. Urethane resin, average particle size 5μm or less
A gas barrier film is characterized in that a film containing an inorganic layered compound having a thickness of 500 nm or less as a main component is formed below.

The present invention provides a gas barrier property under high humidity and a severe bend by forming a film comprising a water-soluble polymer, a water-soluble or water-dispersible urethane resin, and an inorganic layered compound. It has developed a gas barrier film having high adhesion even after the above, and is promising as a highly reliable packaging material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble polymer A in the present invention refers to a polymer which can be completely dissolved or finely dispersed in water at room temperature, and includes, for example, polyvinyl alcohol and its derivatives, cellulose such as carboxymethylcellulose and hydroxyethylcellulose. Derivatives, starches such as oxidized starch, etherified starch, dextrin, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, or their esters, salts and copolymers containing polar groups such as sulfoisophthalic acid Examples include vinyl-based polymers such as polyester, polyhydroxyethyl methacrylate and copolymers thereof, urethane-based polymers, and functional group-modified polymers such as carboxyl groups of these various polymers. Preferably, at least one kind is a polyvinyl alcohol-based polymer or a derivative thereof, and 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, and 60 units of vinyl alcohol. Mol% or more of copolymerized polyvinyl alcohol. The polymerization degree of polyvinyl alcohol and its derivatives is preferably from 100 to 5000,
500-3000 is more preferred.

Further, in the present invention, in addition to the above-mentioned water-soluble polymer, water-soluble or water-dispersible, It is necessary to mix the urethane resin described above, and a surfactant or the like may be used in combination to further improve the stability of the urethane resin in the coating composition.

The urethane resin of the present invention , in particular, the urethane resin produced by reacting a polyol with an isocyanate compound, includes a polyester polymer as a polyol component , and a diisocyanate compound as an isocyanate compound.

The urethane resin in the present invention is preferably a water-soluble or water-dispersible polyester-based urethane resin in view of heat resistance and adhesion. The water-soluble or water-dispersible polyester-based urethane resin is produced by reacting a polyester polyol with a polyisocyanate by a conventional method. If necessary, a chain extender is used.

The polyester polyol is obtained by reacting a dicarboxylic acid and a glycol by a conventional method. Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; oxycarboxylic acids such as oxybenzoic acid; and esters thereof. A forming derivative or the like can be used. Ethylene glycol as the glycol component,
Use aliphatic glycols such as 1,4-butanediol, diethylene glycol and triethylene glycol, aromatic diols such as 1,4-cyclohexanedimethanol, and poly (oxyalkylene) glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol. be able to. Although these have a linear structure, they can be made into a branched polyester by using a trivalent or higher ester-forming component.

Examples of polyisocyanates include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, adducts of tolylene diisocyanate and trimethylol propane, hexamethylene diisocyanate and trimethylol Ethane adducts and the like can be mentioned.

The chain extender optionally used in the present invention includes diols containing a pendant carboxyl group and, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol and the like. Glycols or ethylenediamine,
Diamines such as propylene diamine, hexamethylene diamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminocyclohexylmethane, and the like. Examples of the water-dispersible polyester-based urethane resin include those shown in JP-A-61-228030.

In order to improve the adhesion without impairing the gas barrier properties, the content of the water-soluble or water-dispersible urethane resin is preferably from 3 to 70% by weight, more preferably from 5 to 50% by weight.

Further, in the present invention, a crosslinking agent is added to the coating in an amount of 0.1.
It is preferred that the content be from 0.1 to 10% by weight, since high adhesion can be maintained even when left for a long time under high humidity. More preferably, it is 0.05 to 8% by weight.

The crosslinking agent used in the present invention is not particularly limited as long as it has reactivity with at least one of the water-soluble polymer A and the water-soluble or water-dispersible urethane resin. Preferably, an epoxy-based crosslinking agent, an isocyanate-based crosslinking agent, a melamine-based crosslinking agent, and the like are preferably used.

The inorganic layered compound in the present invention is an inorganic compound in which ultrathin unit crystal layers overlap to form one layered particle, and those which swell and cleave in a solvent are preferred. Among these, a clay compound having a swelling property in a solvent is particularly preferably used. Distribution and clay compound having swelling property to solvent in the present invention is a clay compound having the property of unit crystal layers in a coordination water absorption and swelling of the ultra-thin, generally Si ⁴⁺ is O ^2- against and A layer forming a tetrahedral structure and a layer forming an octahedral structure in which Al ³⁺ , Mg ²⁺ , Fe ²⁺ , Fe ^3+, etc. are coordinated to O ²⁻ and OH ⁻ . They are combined one by one or two to one and stacked to form a layered structure, which may be natural or synthetic. Typical examples are kaolinite, halloysite, montmorillonite, vercurite, dickite, nacrite, antigolite, pyrophyllite, hectorite, beidellite, margarite, talc, tetrasilyl mica, muscovite, and phlogopite. And chlorite. In the present invention, as the size of the inorganic layered compound , the average particle size is 5 μm or less, and the thickness is 500 nm or less .
are doing.

The mixing ratio of (water-soluble polymer A + water-soluble or water-dispersible urethane resin) / layered compound in the present invention is preferably in the range of 10/90 to 95/5 by weight. When it is smaller than 10/90, the strength (elongation, flexibility and pinhole property) of the coating is poor, and when it is larger than 95/5, the gas barrier property at high humidity is greatly reduced.

In the present invention, the thickness of the coating is not particularly limited, but from the viewpoint of a gas barrier film, the thickness of the coating is 0.1 to 0.1.
10 μm is preferred, and 0.3 to 6 μm is particularly preferred.

The coating may contain various additives as long as the gas barrier properties are not impaired. For example, antioxidants, weathering agents, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, coloring agents and the like. Further, inorganic or organic particles may be contained as long as the transparency is not impaired. For example, talc, kaolin, calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia,
Mica, calcium phosphate, cross-linked polystyrene particles and the like.

Furthermore, in order to enhance the interaction between the layered compound and the polymer, between the polymer or between the layered compounds, etc. in forming the film, a divalent or higher valent metal salt, a catalyst component, or the like may be added. It is desirable to use an acetate, a sulfate, a nitrate, or the like containing calcium, magnesium, aluminum, or the like because moisture resistance is improved. The amount is about 1 to 10000 ppm based on the coating.

In the present invention, defining the surface roughness parameter Rt / Ra of the coating surface improves the process abrasion resistance and the gas barrier property when laminating an unstretched propylene film or the like with an adhesive therebetween. It is preferred. Rt is the maximum height, the distance between the maximum peak and the deepest valley of the surface roughness curve, and Ra is the center line average roughness. The surface roughness parameter Rt / Ra is desirably 20 or less, and more desirably 15 or less. If the surface roughness parameter Rt / Ra exceeds 20, the gas barrier properties will decrease. This is when the film is formed at high speed,
It is considered that this is because the film surface is shaved due to contact with the roll or contact between the films during winding. As a method for setting the surface roughness parameter Rt / Ra to 20 or less,
A method of forming a smooth base material by containing inorganic or organic particles having a uniform particle size and forming a coating film dried on the base material at a temperature of 160 ° C. or less in a short time of 15 seconds or less is used. Can be The details of the parameters are described in Jiro Nara, "Method of Measuring and Evaluating Surface Roughness" (General Technology Center, 1983).

The thermoplastic resin base film used in the present invention is necessary mainly for imparting mechanical properties and processability of the film, and includes various commercially available thermoplastic resin films. The thermoplastic resin is not particularly limited, but typical examples thereof include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyamides such as nylon 6, nylon 12, and the like. Polyvinyl chloride, ethylene-vinyl acetate copolymer or saponified product thereof, polystyrene, polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, aromatic polyamide, polyimide, polyamideimide, cellulose, cellulose acetate, polyvinylidene chloride, polyacrylonitrile, polyvinyl alcohol And copolymers thereof. Polyesters such as polyethylene terephthalate and polyolefins such as polyethylene and polypropylene are preferred from the viewpoints of cost performance, transparency, gas barrier properties and the like.

In particular, in order to obtain a packaging film excellent in both oxygen and water vapor barrier properties, the thermoplastic resin base film is preferably an olefin resin.

In the present invention, the atomic ratio of nitrogen to carbon (N / C) on the surface of the substrate film on the coating layer side is determined in consideration of gas barrier properties, adhesiveness of the coating film, technical problems, and the like.
It is preferable that it is in the range of 0.001 to 0.1. It is more preferably in the range of 0.0015 to 0.08, particularly preferably in the range of 0.002 to 0.05. The value of N / C on the surface A can be determined by measuring an X-ray photoelectron spectroscopy (ESCA) spectrum. In order to determine the N / C value of the film on which the coating film is formed, the spectrum may be measured after removing the coating film by hot water treatment or sputtering, but the ESCA spectrum is measured while performing ion etching or the like. The composition distribution from the surface to the depth direction was examined, and the depth at which the number of nitrogen atoms reached a maximum near the interface between the coating film and the base film was defined as A surface, and the N / C was determined from the spectrum at that depth.
Is preferably used. When the maximum is not taken, the A-plane can have a depth of 1/2 of the sum of the maximum value and the minimum value near the interface. Further, a method of measuring the composition distribution in the depth direction using a secondary ion mass spectrometer (SIMS) to obtain N / C is also preferably used.

These thermoplastic resin base films may be any of unstretched, uniaxially stretched and biaxially stretched, but are preferably biaxially stretched from the viewpoints of dimensional stability and mechanical properties. Various additives may be contained in the thermoplastic resin base film. For example, antioxidants, weathering agents, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, coloring agents and the like. Further, inorganic or organic particles may be contained as long as the transparency is not impaired. For example, talc, kaolin, calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia, mica, calcium phosphate, crosslinked polystyrene particles, and the like. The average particle size is preferably 0.001 to 10 μm, and more preferably 0.003 to 5 μm. The average particle size is 10,000 to 10,000 using a transmission microscope or the like.
This is the particle diameter obtained by taking a photograph of 0 times and calculating the number average.

Further, these thermoplastic resin base films are preferably transparent. Light transmittance is 40
% Or more, more preferably 60% or more. The thermoplastic resin base film is preferably smooth. Rt / Ra is preferably 20 or less, and more preferably 15 or less. The thickness of the thermoplastic resin base film is not particularly limited, but is preferably 2 to 1000 μm.

Next, a typical method for producing the gas barrier film of the present invention will be described.

The method for forming the coating on the thermoplastic resin base film is not particularly limited, and an extrusion laminating method or a melt coating method may be used. It is preferable to apply a gravure coat, a reverse coat, a spray coat, a kiss coat, a die coat, or a metaling bar coat to a dispersion solution in which the above components are dispersed in various solvents. Prior to coating, the thermoplastic resin base film may be subjected to a known adhesion promoting treatment, for example, a corona discharge treatment in air or other atmosphere, a flame treatment, an ultraviolet treatment, or the like. When a biaxially stretched film of polyester such as polyethylene terephthalate or polyolefin such as polypropylene is used as the thermoplastic resin base film, either off-line coating or in-line coating may be used.

The method for drying the film is not particularly limited, and a hot roll contact method, a heat medium (air, oil, etc.) contact method, an infrared heating method, a microwave heating method, and the like can be used. The drying of the coating
From the viewpoint of gas barrier properties, the drying is preferably performed within a range of 100 ° C to 170 ° C.
30 seconds, preferably 3 to 15 seconds.

The coating composition containing the components of the film is a solution in which the water-soluble polymer A and the water-soluble or water-dispersible polymer B are uniformly dissolved or dispersed in a solvent and the layered compound is uniformly dispersed or swollen. preferable. As the solvent, water or a mixed solution of water / lower alcohol is used. From the viewpoint of gas barrier properties under high humidity, adhesion of a coating film, and productivity, water / water is used.
It is preferable to use a lower alcohol mixed solution. The lower alcohol is an alcoholic compound having a linear or branched aliphatic group having 1 to 3 carbon atoms, and for example, methanol, ethanol, n- or iso-propanol is preferably used. The mixing ratio of water / alcohol is preferably from 99/1 to 20/80 by weight. If the mixing ratio is more than 99/1, there are problems such as insufficient gas barrier properties under high humidity, poor adhesion between the coating layer and the substrate, and a decrease in productivity. The dispersibility in is deteriorated.

In order to impart coatability to the film, the mixed solvent may contain another water-soluble organic compound as the third component as long as the stability of the dispersion solution is maintained. Is also good. Examples of the water-soluble organic compound include alcohols such as methanol, ethanol, n- or iso-propanol, glycols such as ethylene glycol and propylene glycol, methyl cellosolve,
Examples include glycol derivatives such as ethyl cellosolve and n-butyl cellosolve, polyhydric alcohols such as glycerin and waxes, ethers such as dioxane, esters such as ethyl acetate, and ketones such as methyl ethyl ketone.
Further, the pH of the dispersion solution is from 2 to 11 in view of the stability of the solution.
Is preferred.

The method for adjusting the coating agent is not particularly limited,
A method in which the water-soluble polymer A and the water-soluble or water-dispersible urethane resin are uniformly dissolved in a solvent and then mixed with a solution in which the layered compound is uniformly dispersed is effectively used. Further, the solution may contain a crosslinking agent, particles, and the like.

[0036]

[Evaluation method of characteristics] The evaluation method of characteristics used in the present invention is as follows.

(1) Gas Barrier Property The oxygen permeability was measured using an oxygen permeability measuring apparatus (OX-TRAN100, manufactured by Modern Control) according to ASTM D-3985. The measurement conditions were a temperature of 23 ° C,
The relative humidity is 80%.

(2) Adhesion between the coating film and the substrate before and after the durability test (before the durability test) An unstretched polypropylene film (CPP, T3501, 50 μm, manufactured by Toray Synthetic Film Co., Ltd.) using a polyurethane-based adhesive It was stuck to the coating surface and left at 40 ° C. for 48 hours. Then, the respective surfaces opposite to the surface in contact with the adhesive were reinforced with cellophane tape and cut to a width of 15 mm, and the CPP and the present film were peeled 180 ° using Tensilon, and the peel strength at that time was determined. The peeling was performed at a peeling rate of 10 cm / min and in an atmosphere at 25 ° C. and a relative humidity of 60%.

(After endurance test) Unstretched polypropylene film (CPP, T3501, 50 μm, manufactured by Toray Synthetic Film Co., Ltd.) was adhered to the coating surface of this film using a polyurethane adhesive and left at 40 ° C. for 48 hours. 100 in a Gelboflex tester at 25 ° C.
Gelbo repetitions (reciprocation cycle: 40 times / minute) were performed. Then, the respective surfaces opposite to the surface in contact with the adhesive were reinforced with cellophane tape and cut to a width of 15 mm, and the CPP and the present film were peeled 180 ° using Tensilon, and the peel strength at that time was determined. The peeling was performed at a peeling speed of 10 cm.
/ Min, in an atmosphere at 25 ° C. and a relative humidity of 60%.

(3) Adhesion between coating film and substrate under high humidity Unstretched polypropylene film (CPP, T350 manufactured by Toray Synthetic Film Co., Ltd.) using a polyurethane-based adhesive
1, 50 μm) and the coating surface of this film.
After standing at 0 ° C. for 48 hours, the sample was further subjected to 96% at 90% relative humidity.
Left for hours. Then, each surface on the opposite side to the surface in contact with the adhesive is reinforced with cellophane tape, cut into 15 mm widths, and
The film was peeled 180 ° using Tensilon, and the peel strength at that time was determined. The peeling was performed at a peeling rate of 10 cm / min and in an atmosphere at 25 ° C. and a relative humidity of 60%.

[0041]

The present invention will be described in detail with reference to the following examples. The properties of the obtained film are shown in Table 1.

Example 1 As a water-soluble polymer A, polyvinyl alcohol (hereinafter abbreviated as PVOH) having a saponification degree of 98.5 mol% and a polymerization degree of 2400, and a polyester urethane aqueous solution "Hydran" HW350 "(Dainippon Ink Chemicals) as a urethane resin (Manufactured by Kogyo Co., Ltd.) at a weight ratio of 80:20 and both components are 5 w
water / isopropyl alcohol (hereinafter IP)
A) It was dispersed in a solution (weight ratio 90/10) (Solution X).
Montmorillonite (Kunimine Kogyo Co., Ltd., Kunipia-F) as a layered compound was dispersed in water to a concentration of 3 wt% (Y liquid). Liquid X and liquid Y are mixed so that the mixing ratio of water-soluble polymer A + urethane resin / montmorillonite becomes 50/50 by weight, isopropyl alcohol is 10 wt% with respect to all coating agents, and solid content concentration is 2.5 wt. % Was prepared. A reverse coater (coating speed 60 m / min.) Was applied to a polyester film ("Lumirror", manufactured by Toray Co., Ltd., 12 μm in thickness) which had been subjected to corona discharge surface treatment of the coating material.
, And introduced into a hot-air drying dryer, dried at 140 ° C. for 10 seconds under low tension, and wound up. The film thickness of the obtained film was 0.5 μm, and other characteristics are shown in Table 1. A film excellent in gas barrier properties and adhesion after the durability test was obtained.

Examples 1 to 5 and Comparative Example 4 Films were obtained in the same manner as in Example 1 except that the coating composition, coating thickness and substrate were changed. Table 1 shows the properties of the obtained film.

In Comparative Example 4 , a polyether-based polyurethane aqueous solution “Elastron” H-38 was used as the urethane resin.
When the coatings shown in Table 1 were obtained in the same manner as in Example 1 using (Daiichi Kogyo Seiyaku Co., Ltd.), the adhesion was slightly reduced.

In Example 2 , as shown in Table 1, the melamine-based crosslinking agent (N-methylolated melamine (MW-12LF,
Because of the use of Sanwa Chemical Co., Ltd.), a film having particularly excellent moisture resistance and adhesion was obtained.

In Example 3 , a substrate was subjected to corona discharge treatment (treatment intensity = 60 W) with a biaxially stretched polypropylene film (thickness: 15 μm, surface layer: 3 μm, mixed with ethylene-propylene copolymer and nitrogen gas / carbonic acid mixed gas (volume ratio: 83:17)).・
min / m ² ), synthetic mica (tetrasilyl mica (NA-TS), manufactured by Topy Industries, Ltd.), polyester urethane aqueous solution “Hydran” HW350 ”(Dainippon Ink Co., Ltd.) as urethane resin After applying the coating agent of Table 1 using a reverse coater (coating speed: 50 m / min) using a chemical industry), it was introduced into a hot-air drying dryer and dried under low tension at 110 ° C. for 15 seconds. Was wound up, but as can be seen from comparison with Comparative Example 2, the adhesion was greatly improved.

In Example 4 , as water-soluble polymer A, PVOH having a saponification degree of 98.5 mol% and a polymerization degree of 2400, synthetic mica (tetrasilyl mica (NA-TS), manufactured by Topy Industries, Ltd.), urethane resin A film similar to that of Example 1 was obtained by using a polyester urethane aqueous solution “Hydran” HW350 ”(manufactured by Dainippon Ink and Chemicals, Inc.) with the composition shown in Table 1. Gas barrier properties and adhesion after a durability test were obtained. An excellent film was obtained.

In Example 5 , when a film provided with the coating agent shown in the table was prepared, good barrier properties and adhesion were obtained.

Comparative Example 1 A film shown in Table 1 was obtained in the same manner as in Comparative Example 4 , except that a coating composition of 2.5 wt% was prepared using only the X solution.
It was found that the obtained film had poor gas barrier properties.

Comparative Example 2 A film shown in Table 1 was obtained in the same manner as in Example 3 except that the urethane resin was not added to the liquid X, but the adhesion was poor.

Comparative Example 3 A melamine-based crosslinking agent (N-
A film shown in Table 1 was obtained in the same manner as in Example 3 except that only methylolated melamine (MW-12LF, manufactured by Sanwa Chemical Co., Ltd.) was added, but the adhesion was poor.

[0052]

[Table 1] The meanings of the abbreviations in the table are as follows.

PET: biaxially oriented polyethylene terephthalate PP: biaxially oriented polypropylene (thickness: 15 μm, surface layer: 3 μm, corona discharge treatment with ethylene-propylene copolymer and mixed gas of nitrogen gas / carbonic acid (volume ratio: 83:17) (treatment intensity = 60 W · min / m ² ) PVOH: polyvinyl alcohol urethane resin 1: polyester-based urethane aqueous solution “Hydran” HW350 (manufactured by Dainippon Ink and Chemicals, Inc.) urethane resin 2: polyether-based polyurethane aqueous solution
Elastron "H-38 (Daiichi Kogyo Seiyaku Co., Ltd.) Crosslinking agent 1: Melamine-based crosslinking agent (N-methylolated melamine (MW-12LF, manufactured by Sanwa Chemical Co., Ltd.)) Crosslinking agent 2: γ- (2- Aminoethyl) aminopropyltrimethoxysilane Layered particle 1: Montmorillonite (Kunimine Industry Co., Ltd., Knipia-F) Layered particle 2: Synthetic mica (tetrasilyl mica (N
A-TS), manufactured by Topy Industries, Ltd.)

[0054]

The film obtained by the present invention not only has excellent durability, but also exhibits excellent gas barrier properties and adhesion even under high humidity, so that it can be used as any packaging material. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI B32B 27/40 B32B 27/40 C08L 29/02 C08L 29/02 75/06 75/06 (56) References 51469 (JP, A) JP-A-3-93542 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J ^7/ 04-7/06 B32B 27/00-27/42

Claims (3)

(57) [Claims] A water-soluble polymer A and a water-soluble or water-dispersible water-soluble polymer A on at least one surface of a thermoplastic resin base film.
Polyester urethane resin and average particle size of 5μm or less
A gas barrier film, characterized in that a film containing an inorganic layered compound having a thickness of 500 nm or less as a main component is formed. 2. A coating composition containing 0.01 to 10% by weight of a crosslinking agent.
The gas barrier film according to claim 1, characterized in that it contains. 3. The method according to claim 1, wherein the base film is an olefin resin.
The gas barrier film according to claim 1 or claim 2, characterized in that Ranaru.