JP4836623B2 - Gas barrier film and gas barrier laminate - Google Patents

Description

  The present invention relates to a gas barrier film and a gas barrier laminate material that are used in the packaging field of foods, pharmaceuticals, precision electronic components, etc., and have excellent gas barrier properties, particularly oxygen barrier properties, and excellent appearance, transparency, and the like. .

In recent years, packaging materials used in the packaging field of foods, pharmaceuticals, precision electronic components, etc. are used to maintain the taste and freshness by suppressing the alteration of contents, especially the oxidation of fats and oils and the alteration of proteins in foods. In addition, in pharmaceuticals, the effects of oxygen permeating through packaging materials are prevented in order to suppress the deterioration of active ingredients and maintain their efficacy, and in precision electronic parts, to suppress the corrosion of metal parts and prevent poor insulation. Therefore, it is required to have a gas barrier property to block gas (gas).
Therefore, a packaging using a polymer film, which is generally said to have a relatively high gas barrier property, such as polypropylene (KOP), polyethylene terephthalate (KPET) or ethylene vinyl alcohol copolymer (EVOH) coated with vinylidene chloride resin as a gas barrier film. A packaging film using a film or a vapor-deposited film in which a silicon oxide thin film such as silicon oxide (SiOx) is provided on a substrate made of a transparent polymer by means such as vacuum vapor deposition has been generally used. .

However, packaging films using EVOH are easily affected by temperature and humidity, and depending on the changes, the gas barrier properties may be further lowered. Packaging films using vinylidene chloride resins such as KOP and KPET are used after use. Since incineration in the disposal of waste gas generates chlorine gas, it is said that this is one of the causes of acid rain, and recently there is a tendency to avoid it.
In addition, a deposited film in which a silicon oxide thin film is provided on a substrate made of a transparent polymer by means such as vacuum deposition may easily crack the deposited film due to bending or the like, and as a result, gas barrier properties may be lowered.

Therefore, as a packaging film that overcomes these drawbacks, a hydrophilic polymer solution such as polyvinyl alcohol (PVA) is used as a method for coating a film with a liquid composition comprising a water-soluble inorganic substance or polymer to develop a high gas barrier property. And a hydrolyzed solution of metal alkoxide, a film is coated, dried, and heat treated to allow gas barrier properties to be imparted by causing interaction between the hydrophilic polymer and the metal alkoxide (Patent Document 1). . These methods combine the excellent gas barrier properties of metal oxides with the flexibility of polymers, and have high gas barrier properties and practicality that can withstand rough handling such as bending.
Furthermore, in place of polyvinyl alcohol, there are also reports such as those using a mixture of ethylene-vinyl alcohol copolymer with polyvinyl alcohol (Patent Document 2), those using modified polyvinyl alcohol as polyvinyl alcohol (Patent Document 3), etc. In addition, a method of using an alkoxysilane having an imino group as a silane compound and aging after drying to form a gas barrier layer (Patent Document 4) has also been reported.

However, these barrier coat layers and plastic substrates do not have practically sufficient adhesive strength, and when used as a gas barrier film, it is necessary to provide an adhesive layer between the barrier coat layer and the plastic substrate. When the adhesive layer is provided, the volume change before and after drying due to evaporation of the solvent of the metal alkoxide hydrolyzate is very large in the step of drying the barrier coat layer containing the hydrolyzed solution of the metal alkoxide on the adhesive layer. Since the stress is concentrated, the adhesive layer cannot withstand the shrinkage force on the soft uncured adhesive layer having a low elastic modulus, and the barrier coat layer is cracked to form a dense film. It was difficult and caused a decrease in barrier properties. For this reason, in order to develop a good gas barrier property, there is a problem that precise control such as temperature and humidity control in the drying process is required, and the work becomes complicated.
In addition, in the process of laminating the gas barrier film with the sealant film, if the elastic modulus of the adhesive layer between the base film and the barrier coat layer is low, the adhesive layer is plastically broken by the heat and tension in the process, and the barrier coat layer is formed. There was a problem of cracks.
JP-A-4-345841 and JP-A-6-192454 JP 2001-219506 A JP 2004-143197 A JP 2002-292810 A

  The present invention solves the above-mentioned conventional drawbacks, can exhibit gas barrier properties under a wide range of drying conditions, and can sufficiently withstand mechanical and thermal stress during lamination. An object of the present invention is to provide an inexpensive gas barrier film and gas barrier laminate having a gas barrier layer that has a strong adhesion strength of a coating film and has a gas barrier property, particularly an oxygen barrier property.

The present inventors have found that by adding an inorganic filler to the adhesive layer, it is possible to obtain a rigid adhesive layer having a high elastic modulus and solve the problem, and the present invention has been achieved.
That is, the present invention
(1) A gas barrier film in which an adhesive layer and a barrier coat layer are laminated in this order on one side of a substrate made of a plastic film, wherein the barrier coat layer is a hydrolyzate of alkoxysilane and / or alkoxysilane polycondensate And a mixture of polyvinyl alcohol (weight ratio of silicon oxide produced from a hydrolyzate of alkoxysilane and / or polycondensate of alkoxysilane and polyvinyl alcohol is 60/40 to 80/20), and the adhesive layer Gas barrier film having an oxygen permeability of 10 cc / m ² · atm · 24 h or less under 20 ° C.-90% RH condition, wherein an inorganic filler is added in an amount of 1-30 wt% relative to the adhesive layer,
(2) The gas barrier film according to the above (1), wherein the inorganic filler is silica particles,
(3) The gas barrier film according to the above (1) to (2), wherein the adhesive layer is a two-component curable urethane adhesive,
(4) The gas barrier film according to any one of (1) to (3), wherein the plastic film is a stretched polyamide film, a stretched polypropylene film, or a stretched polyester film,
(5) A gas barrier laminate in which a sealant layer is further laminated on the sealant layer of the gas barrier film according to any one of (1) to (4) above,
(6) The gas barrier laminate according to (5) above, wherein the sealant layer is laminated by a dry lamination method or an extrusion lamination method,
(7) The gas barrier laminate according to any one of (5) to (6), wherein the sealant layer is unstretched polyethylene or unstretched polypropylene film.
Is to provide.

According to the present invention, since the adhesive layer has a high elastic modulus and is rigid, it suppresses shrinkage in the width direction of the barrier coat layer, prevents cracks, and shrinks in the thickness direction. It is capable of withstanding mechanical and thermal stress during lamination, has excellent gas barrier properties, especially oxygen barrier properties, and is flexible, transparent, moisture resistant, and solvent resistant. A gas barrier film having a gas barrier layer and a gas barrier laminate.
Moreover, since the adhesion strength of the coating film is strong, there is also an effect that a gas barrier film and a gas barrier laminate material having a good appearance without cracks can be provided at low cost.

Hereinafter, the present invention will be described in detail.
The alkoxysilane and its polycondensate used in the present invention are represented by the following general formula [1]. In the formula, n is an integer of 1 to 10, and R is an alkyl group having 1 to 4 carbon atoms, which may be the same or different. Moreover, these mixtures may be sufficient.

The polyvinyl alcohol used in the present invention is not particularly limited, but 80% or more of saponified product is preferable, and complete saponification is more preferably used. Complete saponification has better compatibility with a hydrolyzate obtained by hydrolyzing alkoxysilane, and forms a denser barrier layer.
The degree of polymerization of polyvinyl alcohol is preferably 200 to 3,500.

The plastic film used in the present invention is a polyolefin resin such as polyethylene or polypropylene; a polyester resin such as polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate or polybutylene terephthalate; a polyether such as polyoxymethylene Polyamide resins; Polyamide resins such as polyamide-6, polyamide-6,6, polymetaxylene adipamide; Vinyl resins such as polystyrene, poly (meth) acrylic ester, polyacrylonitrile, polyvinyl acetate; Polycarbonate resins Cellulosic resin such as cellulose acetate; Polyimide; Polyetherimide; Polyphenylene sulfide; Polyethersulfone; Polysulfone; Polyetheretherketo ; As a main component a thermoplastic resin such as polyether ketone ketone. These thermoplastic resins may be a homopolymer or a copolymer. In addition, the plastic film used for this invention is not limited to the said thermoplastic resin, The non-thermoplastic film represented by the cellophane can also be used.
As the base material of the present invention, those obtained by molding these resins into a film shape are used. Either unstretched film or uniaxially or biaxially stretched can be used, but stretched polyamide film, stretched polypropylene film or stretched polyester film is the most preferred from the viewpoint of ease of coating when coating the barrier layer and the strength of the barrier material. preferable.

The gas barrier film of the present invention is obtained by laminating an adhesive layer and a barrier coat layer in this order on one side of a substrate made of a plastic film.
As an adhesive that can be used for the adhesive layer, a general adhesive can be used as long as it does not interfere with the dispersion of the inorganic filler. As an adhesive, a compound containing a carboxyl group, an acid anhydride group, an oxazolinyl group, a thioisocyanate group, an epoxy group, specifically, a polyester polyol-based adhesive, a polyether polyol-based adhesive, Examples include polyurethane polyol-based adhesives, polyether polyurethane polyol-based adhesives, polyester polyurethane polyol-based adhesives, oxazoline-containing polymer-based adhesives, epoxy-based adhesives, etc. Among them, two-component curable urethane-based adhesives are preferable. .

An inorganic filler is added to the adhesive layer.
The inorganic filler to be used is not particularly limited as long as the desired hardness (elastic modulus) and transparency can be obtained by uniformly finely dispersing in the adhesive layer, and specifically, silica, talc, alumina, unmoney. And calcium carbonate, and silica particles are particularly preferable.
These inorganic fillers can be used both untreated and treated.
The addition amount of the inorganic filler is 1 to 30 parts by weight, preferably 3 to 30 parts by weight with respect to 100 parts by weight of the adhesive layer. If the added amount of the inorganic filler is less than 1 part by weight, the desired effect cannot be obtained. Moreover, when there are more addition amounts of an inorganic filler than 30 weight part, problems, such as a transparency fall, will arise.
As a dispersion method of the inorganic filler, a normal dispersion method such as dispersion by mechanical shearing, dispersion by ultrasonic waves, or the like can be used.

Application and drying of the adhesive layer on the plastic film can be performed by known methods such as reverse roll coating, dip coating, Mayer bar coating, knife coating, nozzle coating, die coating, spray coating, and curtain coating. Various printing methods such as a printing method, screen printing, and gravure coating may be mentioned.
The thickness of the adhesive layer after drying is 0.03 to 0.40 μm, preferably 0.06 to 0.20 μm. When the thickness is less than 0.03 μm, sufficient adhesive strength is not exhibited. On the other hand, when the thickness exceeds 0.40 μm, the transparency is lowered and the cost is increased.

The barrier coat layer laminated on the adhesive layer in the present invention is a mixture of the alkoxysilane and / or alkoxysilane polycondensate hydrolyzate represented by the general formula [1], and a polyvinyl alcohol solution. It is obtained by coating.
A hydrolysis solution of an alkoxysilane and an alkoxysilane polycondensate can be prepared by heating the alkoxysilane and the alkoxysilane polycondensate in a solution containing water, an acid and an organic solvent. At this time, polycondensation of the alkoxysilane hydrolyzate also occurs simultaneously. The amount of water used is 6 to 10 moles per silicon atom of alkoxysilane. When the amount is more than 10 mol, polycondensation of the hydrolyzed silicate proceeds too much and the solution gels. The gelled liquid cannot be uniformly mixed with the polyvinyl alcohol solution used in the present invention. On the other hand, when the amount is less than 6 mol, hydrolysis of the alkoxysilane cannot proceed and it is practically difficult to obtain a uniform solution.
As the acid which acts as a catalyst for hydrolysis and polycondensation of alkoxysilane and alkoxysilane polycondensate, mineral acids such as hydrochloric acid and nitric acid and other inorganic acids are preferably used. The pH during hydrolysis is preferably 0.5 to 4.5, more preferably 2.0 to 4.0. If the pH is greater than 4.5, hydrolysis does not proceed. When the pH is less than 0.5, hydrolysis proceeds sufficiently, but at the same time, polycondensation proceeds remarkably and the solution gels. The temperature during hydrolysis is 30 to 60 ° C, preferably 40 to 55 ° C. If it is higher than 60 ° C., polycondensation proceeds and the solution gels. On the other hand, if the temperature is lower than 30 ° C., hydrolysis does not proceed sufficiently and a longer time is required, which is not practical. The hydrolysis time varies depending on the pH and temperature of the solution, but is generally 30 to 400 minutes.
As the organic solvent used in the hydrolysis, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like are used, and ethyl alcohol and isopropyl alcohol are particularly preferably used.

Mixing the hydrolyzate of alkoxysilane and alkoxysilane polycondensate with polyvinyl alcohol provides a gas barrier film having a high oxygen barrier property even under high humidity, so that silicon oxide in the barrier coat layer (in terms of SiO ₂ ) And the weight ratio of polyvinyl alcohol must be 100 parts by weight: 25 to 110 parts by weight, preferably 100 parts by weight: 30 to 65 parts by weight. When the weight ratio of polyvinyl alcohol is lower than 25 parts by weight, not only the flexibility of the barrier layer is sufficient and cracks are easily generated, but also the gas barrier property is lowered. When it is larger than 110 parts by weight, the gas barrier property is also lowered.

In order to apply the barrier coat layer coating solution thus prepared to a substrate made of a plastic film, a normal coating method can be used. For example, various printing methods such as reverse roll coating method, dip coating method, Mayer bar coating method, knife coating method, nozzle coating method, die coating method, spray coating method, curtain coating method, screen printing, gravure coating, etc. .
The barrier coat layer thickness after drying is 0.1 to 3.0 μm, preferably 0.3 to 1.5 μm. When the thickness is less than 0.1 μm, sufficient gas barrier properties are not exhibited. On the other hand, if the thickness exceeds 3.0 μm, the gas barrier property is lowered and the cost is increased due to the occurrence of cracks and insufficient adhesion strength.

  The barrier coat layer is dried and aged after application to form a barrier coat layer having a high gas barrier property even under high humidity. Drying is performed at a dryer internal temperature of 150 ° C. or lower, preferably 50 to 120 ° C. for 1 to 30 seconds. When dried at a temperature higher than 150 ° C. or when the drying time is longer than 30 seconds, the volumetric shrinkage of the coating film becomes remarkable, resulting in cracks in the coating film, not only deteriorating the appearance but also reducing the gas barrier properties. Further, after drying, aging is performed at an ambient temperature of 20 to 80 ° C. for 24 hours or longer, preferably 40 to 60 ° C. for 36 hours or longer. When the temperature is higher than 80 ° C., the flatness of the base material made of a plastic film is impaired, and processing suitability such as printability is deteriorated. Moreover, when it is lower than 20 ° C., a sufficient aging effect cannot be obtained. By this aging treatment, the barrier layer is densified and a strong interaction mainly consisting of hydrogen bonds of silicate and polyvinyl alcohol is formed, and the gas barrier property is not deteriorated over time under high humidity. A film is obtained.

The gas barrier film of the present invention has an oxygen permeability of 10 cc / m ² · atm · 24 h or less under 20 ° C.-90% RH condition.
If the oxygen permeability exceeds this, sufficient oxygen barrier properties may not be exhibited if the oxygen permeability is kept for a long time under high humidity.

In the present invention, there is further provided a gas barrier laminate in which a sealant layer is laminated on the barrier coat layer of the gas barrier film.
The sealant layer is not limited as long as it is a layer mainly composed of a film having a melting point lower than that of the gas barrier film. For example, polyethylene, polypropylene, acid-modified polyethylene, acid-modified polypropylene, an ethylene copolymer containing an acrylic acid or methacrylic acid derivative, It may be a single layer film made of dendrites such as ionomers, or a multilayer made of two or more of these resins. Specifically, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, etc. are used as polyethylene, and homo-type polypropylene, random-type polypropylene, block-type polypropylene are used as the polypropylene, and acid-modified polypropylene resin. As random type polypropylene grafted with unsaturated carboxylic acid, homotype polypropylene, block type polypropylene or the like, and as acid-modified polyethylene resin, linear low density polyethylene, high density polyethylene grafted with unsaturated carboxylic acid or Examples thereof include ethylene copolymers containing medium density polyethylene, acrylic acid or methacrylic acid derivatives.
Among these, unstretched polyethylene films and unstretched polypropylene films are particularly preferable.

The sealant layer is laminated on the substrate by a method known per se, such as a dry lamination method or an extrusion lamination method.
Known adhesives can also be used. For example, in the dry laminating method, a two-component curing type polyester polyol adhesive, polyether polyol adhesive, polyurethane polyol adhesive, polyether polyurethane polyol adhesive, polyester polyurethane polyol In the extrusion laminating method, an imine type, a titanate type, an ester type, a urethane type and the like are exemplified as the system adhesive.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
In addition, the apparatus and conditions used for the measurement of each physical property are as follows.

Oxygen permeability measurement An oxygen permeability measuring apparatus model 8000 manufactured by Illinois was used.
The measurement was performed at 20 ° C.-90% RH for 48 hours.

-Dry laminate suitability evaluation As an evaluation of dry laminate suitability, a heat resistance test of a gas barrier film under a certain tension was performed.
That is, a tension of 2.0 kg / m was applied in the film flow direction of the gas barrier film, and the appearance of the gas barrier film after observation for 1 minute at various temperatures was observed.

Extrusion lamination suitability evaluation As a sealant film, linear low density polyethylene 30 μm (manufactured by Tosero Co., Ltd .; TUX MCS), extrusion resin thickness 20 μm, extrusion resin temperature 300 ° C., gas barrier film and sealant film are added to molten resin The state of the appearance of the gas barrier film was observed by changing the weight of the pressure processing step to 0.20 to 0.35 kg / m.

・ Peel strength Using dry laminate adhesive TM-265 / CAT-RT37 (manufactured by Toyo Morton), linear low density polyethylene 50 μm (manufactured by Toh cello; TUX FCD), laminate, tensile test Using a machine (TENSILON RTA-100 manufactured by ORIENTEC), measurement was performed at a tensile speed of 100 mm / min and a film width of 15 mm.

-Transparency evaluation Haze was measured by using Haze Meter NDH2000 manufactured by NIPPON DENSHOKU by the haze measurement method of transparent plastic material of JIS K7136.

Example 1
The 1.2 times of ethanol was added relative to the weight of pure water and the silicon oxide of 8.3 mols per mol of the silicon 1 atom of ethyl silicate 40 (Colcoat Co. SiO ₂ minutes 40% pentamer), 1N After adjusting the pH to 2.8 using hydrochloric acid, hydrolysis was performed at 50 ° C. for 3.5 hours with stirring. After cooling this solution, pure water was added to obtain a transparent solution having a silicon oxide concentration of 8% by weight. Further, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-110, saponification degree 98-99%, average polymerization degree 1000) was dissolved in pure water to obtain an aqueous solution having a concentration of 7% by weight. The above solution was mixed and stirred so that the weight ratio of silicon oxide to polyvinyl alcohol was 70/30 to obtain a barrier coating solution. Next, as an adhesive adjustment, a two-component curable adhesive AD-335AE / CAT-60 (manufactured by Toyo Morton Co., Ltd.) has a concentration of 3.5% by weight and a solid content ratio of AD-335AE / CAT-60 = 1.00 / After adjusting with ethyl acetate and toluene so as to be 2.35, silica particles subjected to surface hydrophobization treatment of 12.3 parts by weight with respect to 100 parts by weight of the adhesive solid content (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) Was added and ultrasonic dispersion was performed to obtain an adhesive.
The above adhesive was coated with a Mayer bar on a stretched nylon film (Kohjin biaxially stretched polyamide film “Bonyl”, thickness 15 μm) and dried at 100 ° C. for 15 seconds to produce an adhesive layer having a thickness of 0.1 μm. . Next, the barrier coating solution was coated on the adhesive layer with a Mayer bar and dried at 110 ° C. for 15 seconds. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer. After returning the film to room temperature, it was aged at 55 ° C. to obtain the gas barrier film of the present invention. The thickness of the coat layer of this film was 1.0 μm.
The film was conditioned at 20 ° C.-90% RH for 48 hours, and the oxygen gas permeability, appearance, peel strength, and haze were measured under the same conditions. The results are shown in Table 1.
Table 2 shows the dry laminate suitability evaluation results, and Table 3 shows the extrusion laminate suitability evaluation results.

Example 2
In Example 1, a film was obtained in the same manner as in Example 1 except that the silica particles were changed to an organosilica sol TOL-ST manufactured by Nissan Chemical Industries. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The film was conditioned at 20 ° C.-90% RH for 48 hours, and the oxygen gas permeability, appearance, peel strength, and haze were measured under the same conditions. The results are shown in Table 1.

Example 3
In Example 1, instead of a stretched nylon film, a stretched polypropylene film (FOK-P manufactured by Futura Chemical Co., Ltd.) was used, and a two-component curable adhesive AD-76H5 / CAT-60 (manufactured by Toyo Morton) was used at a concentration of 10.0. Example 1 except that the weight percentage, the solid content ratio is AD-76H5 / CAT-60 = 3.20 / 1.00, and the amount of silica particles added to 100 weight parts of the adhesive solid content is changed to 20.0 weight parts. A film was obtained in the same manner as above. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The film was conditioned at 20 ° C.-90% RH for 48 hours, and the oxygen gas permeability, appearance, peel strength, and haze were measured under the same conditions. The results are shown in Table 1.

Example 4
In Example 1, a film was obtained in the same manner as in Example 1 except that the stretched nylon film was changed to a stretched polyester film (manufactured by Mitsubishi Chemical Polyester). The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The film was conditioned at 20 ° C.-90% RH for 48 hours, and the oxygen gas permeability, appearance, peel strength, and haze were measured under the same conditions. The results are shown in Table 1.

Comparative Example 1
In Example 1, a film was obtained in the same manner as in Example 1 except that the amount of silica particles added was changed to 40 parts by weight with respect to 100 parts by weight of the adhesive solid content. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The appearance, peel strength, and haze of this film were measured, and the results are shown in Table 1.

Comparative Example 2
In Example 1, a film was obtained in the same manner as in Example 1 except that silica particles were not added. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The appearance state and peel strength of this film were measured, and the results are shown in Table 1.

Comparative Example 3
In Example 1, a film was obtained in the same manner as in Example 1 except that the adhesive layer was not provided. The temperature of the film when the barrier coat layer was dried was 70 ° C. with an infrared thermometer.
The film was conditioned at 20 ° C.-90% RH for 48 hours, and the oxygen gas permeability, appearance, peel strength, and haze were measured under the same conditions. The results are shown in Table 1.

The gas barrier film of the present invention had good appearance, high peel strength, and oxygen gas permeability of 10 cc / m ² · 24 Hr · atm or less even under high humidity. On the other hand, in the case of Comparative Example 1 in which the amount of silica particles added to the adhesive layer was increased, it was found that the appearance, oxygen permeability, and peel strength were good, but the transparency was greatly reduced. . Also. In the case of Comparative Example 2 in which no silica particles were added to the adhesive layer, cracks were generated in the barrier coat layer, and the appearance was remarkably reduced. On the other hand, in the case of Comparative Example 3 without an adhesive layer, good results were obtained with respect to appearance, oxygen permeability, and transparency, but the peel strength was greatly reduced, and practically sufficient strength was not obtained. I understand that.

Comparative Example 4
In Example 1, a film having a good appearance was obtained in the same manner as in Example 1 except that silica particles were not added and the drying conditions at the time of drying the burr coat layer were changed to 80 seconds at 15 seconds. The temperature of the film when the barrier coat layer was dried was 46 ° C. with an infrared thermometer.
Table 2 shows the dry laminate suitability evaluation results of this film, and Table 3 shows the extrusion laminate suitability evaluation results.

The gas barrier film of the present invention can maintain a good appearance even at a high temperature under a constant tension, and can be processed without impairing the appearance even when dry lamination is performed, and the drying temperature Therefore, it can be seen that a laminated material having excellent productivity and residual solvent reduction can be obtained.
In addition, a good appearance can be maintained even when the load is increased in the process of bonding to the molten resin, and even when extrusion lamination is performed, stable processing is performed without impairing the appearance. I understand what I can do.

  As described above, according to the present invention, a gas barrier layer having excellent gas barrier properties, particularly oxygen barrier properties, excellent flexibility, transparency, moisture resistance, solvent resistance, etc., and a good appearance without cracks. Since the gas barrier film and the gas barrier laminate material are provided, it can be suitably used in the packaging field of foods, pharmaceuticals, precision electronic components and the like.

Claims (7)

A gas barrier film in which an adhesive layer and a barrier coat layer are laminated in this order on one side of a base material made of a plastic film, wherein the barrier coat layer is bonded with polyvinyl alcohol after hydrolysis of alkoxysilane and / or alkoxysilane polycondensate. A mixed mixture (alkoxysilane and / or alkoxysilane polycondensate hydrolyzate having a silicon oxide and polyvinyl alcohol weight ratio of 60/40 to 80/20), and inorganic in the adhesive layer Filler is added to the adhesive layer in an amount of 1 to 30 wt%. The oxygen permeability under 20 ° C-90% RH condition is 10cc / m2 · atm · 24h or less, and the gas barrier coat layer is cracked after lamination with the sealant layer. Gas barrier film with a good appearance that does not enter .   The gas barrier film according to claim 1, wherein the inorganic filler is silica particles. The gas barrier film according to claim 1 or 2, wherein the adhesive layer is a two-component curable urethane adhesive.   The gas barrier film according to any one of claims 1 to 3, wherein the plastic film is a stretched polyamide film, a stretched polypropylene film, or a stretched polyester film.   A gas barrier laminate in which a sealant layer is further laminated on the barrier coat layer of the gas barrier film according to claim 1.   The gas barrier laminate according to claim 5, wherein the sealant layer is laminated by a dry lamination method or an extrusion lamination method. The gas barrier laminate according to claim 5 or 6, wherein the sealant layer is unstretched polyethylene or unstretched polypropylene film.