JP2016172328A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having high gas barrier properties as well as high adhesion between layers at a high temperature and a high humidity or after a weather resistance test.SOLUTION: A gas barrier film 5 includes: an anchor coat layer 2 including an inorganic substance and an organic substance; an inorganic oxide layer 3; and an overcoat layer 4 including an organic substance or an organic substance containing an inorganic substance, laminated in this order at least on one side of a polymer film base material 1. The anchor coat layer 2 is composed of a graft copolymer of a (meth)acrylic resin, an isocyanate resin and a modified silicone oil.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film excellent in gas barrier properties and adhesion.

  Gas barrier films are widely used in the fields of precision electronic parts such as hard disks and semiconductor modules, back sheets for solar cells, packaging fields for foods and pharmaceuticals, etc., and parts that need to block oxygen and water vapor in non-packaging fields. It has been.

  For packaging of precision electronic components, a packaging body with gas barrier properties that blocks oxygen and water vapor that permeate the packaging material and other gases that alter the contents to prevent corrosion of metal parts and insulation failure is required. It has been. Moreover, in food packaging applications, it is necessary to be able to maintain the taste and freshness by suppressing the oxidation and alteration of proteins and fats and oils. Moreover, in the packaging use of pharmaceutical products that require handling in a sterile state, it is necessary to suppress the alteration of the active ingredient and maintain the efficacy.

  For this reason, conventionally used packaging materials include metal foils such as aluminum, aluminum vapor deposition films, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), and polyvinylidene chloride, which are not affected by temperature and humidity. Resin films such as (PVDC) and polyacrylonitrile (PAN), and plastic films laminated or coated with these resin films have been used favorably.

  However, a gas barrier resin film or a film coated with a gas barrier resin is highly temperature dependent and cannot maintain high gas barrier properties. Furthermore, PVDC, PAN, and the like have the possibility of causing harmful substances during disposal and incineration after use.

  Packaging materials using metal foils such as aluminum and aluminum vapor deposition films are excellent in gas barrier properties, but they are not retort resistant, and because they are opaque, it is difficult to identify the contents through the packaging material. In addition, it has the disadvantages that it must be treated as an incombustible material at the time of disposal after use, the foreign matter cannot be inspected by a metal detector, and the heat treatment cannot be performed in a microwave oven.

  Further, as a packaging material that overcomes these drawbacks, a gas barrier film in which an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide or the like is vapor-deposited on a transparent base film has recently been put on the market. These gas barrier vapor-deposited films are known to have gas barrier properties such as oxygen and water vapor, although not as much as metal vapor-deposited films. However, these inorganic oxide vapor-deposited films are still unsatisfactory in terms of high gas barrier properties and adhesion strength between layers under high temperature and high humidity (85 ° C. and 85% RH) and after a weather resistance test.

  In addition, there exists a thing of patent document 1 as a technique relevant to this application, for example.

Japanese Patent No. 5103184

  The present invention is intended to solve the above-mentioned problems of the prior art, and an object thereof is to provide a gas barrier film having high gas barrier properties and having high interlayer adhesion even under high temperature and high humidity conditions and after a weather resistance test. And

  The gas barrier film according to the present invention has an anchor coat layer made of an inorganic substance and an organic substance, an inorganic oxide layer, and an overcoat layer made of an organic substance containing an organic substance or an inorganic substance in this order on at least one surface of the substrate. It is a laminated one. The anchor coat layer is made of a graft copolymer of (meth) acrylic resin, isocyanate resin, and modified silicone oil.

  ADVANTAGE OF THE INVENTION According to this invention, while having high gas-barrier property, the gas-barrier film which has high interlayer adhesiveness also under high temperature, high humidity, and a weather resistance test can be provided.

Sectional drawing of the gas-barrier film which concerns on one Embodiment of this invention Sectional drawing of the laminated gas barrier film which concerns on one Embodiment of this invention

  Embodiments of the present invention will be described below.

  FIG. 1 is a cross-sectional view of a gas barrier film according to an embodiment of the present invention. The gas barrier film 5 is obtained by laminating an anchor coat layer 2, an inorganic oxide layer 3, and an overcoat layer 4 in this order on a polymer film substrate 1.

  The polymer film substrate 1 is not particularly limited, and a known one can be used. Examples of the polymer film substrate 1 include polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, Polymeric film base materials such as polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, polyether sulfone, acrylic, and cellulose (triacetyl cellulose, diacetyl cellulose, etc.) can be mentioned, but are not particularly limited.

  It is preferable to use a transparent film as the polymer film substrate 1 because it is suitable for mass production. In addition, the thickness is not particularly limited, and is practically preferably in the range of 6 μm to 188 μm in consideration of workability such as vapor deposition for forming a gas barrier film.

  The anchor coat layer 2 is made of a graft copolymer of (meth) acrylic resin, isocyanate resin, and modified silicone oil. In this specification, the term “(meth) acrylic resin” is used as a general term for both acrylic resin and methacrylic resin. In this specification, the term “(meth) acrylic acid” is used as a general term for both acrylic acid and methacrylic acid.

  As the (meth) acrylic resin constituting the anchor coat layer 2, a copolymer of two or more kinds of (meth) acrylic acid or (meth) acrylic acid ester monomers is used. Examples of (meth) acrylic acid include, but are not limited to, acrylic acid (AA) and methacrylic acid (MAA). Examples of (meth) acrylic acid ester monomers include methyl acrylate (MA), ethyl acrylate (EA), propyl acrylate (PA), butyl acrylate (BA), cyclohexyl acrylate (CHA), methyl methacrylate (MMA), and ethyl. Methacrylate (EMA), propyl methacrylate (PMA), butyl methacrylate (BMA), cyclohexyl methacrylate (CHMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), hydroxyethyl methacrylate (HEMA) , Hydroxypropyl methacrylate (HPMA), hydroxybutyl methacrylate (HBMA) and the like. There. In order to maintain the adhesion between the layers, it is preferable to select one or more from the group of methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate. In the case of a (meth) acrylic acid ester monomer having a hydroxyl group or a carboxyl group, it is preferably introduced because it reacts with isocyanate and improves interlayer adhesion.

  Examples of the isocyanate group-containing resin constituting the anchor coat layer 2 include hexamethylene-1,6-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate, 1 , 3-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Various diisocyanates, and various modified products thereof, and dimer bodies, adduct bodies, allophanate bodies, trimer bodies, carbodiimide adduct bodies, biuret bodies, etc. These polymers, and polymers obtained by adding a polyhydric alcohol. In particular, hexamethylene-1,6-diisocyanate, which has little influence on adhesion to the substrate and yellowing due to ultraviolet rays, is preferred.

  The modified silicone oil constituting the anchor coat layer 2 refers to one having a linear siloxane skeleton and having a group other than hydrogen or a hydrocarbon group in the molecular structure. As modified silicone oil, what is marketed as modified silicone oil can be used. Among these, those having a dimethyl silicone skeleton in the molecular structure are preferable. In addition, in order to improve the durability of the anchor coat layer and the interlayer adhesion with the substrate, the reactive group has a dimethyl silicone skeleton in the molecular structure and can react with the thermosetting resin in the molecular structure. Particularly preferred is a reactive dimethyl silicone oil having The reactive group may be introduced into a part of the side chain of the polysiloxane, may be introduced into one or both ends of the polysiloxane, or the side of the polysiloxane. In addition to the chain, it may be introduced at one or both ends. In particular, those having a reactive group at one end are preferred. When a reactive group at one end reacts, a silicone graft copolymer with a silicone chain hanging from the resin side chain can be obtained, and the resin surface properties such as lubricity, releasability, abrasion resistance, and water repellency Can be modified. By modifying the characteristics of the anchor coat layer surface, the degree of freedom in selecting an acrylic resin or an isocyanate group-containing resin is improved. When using a resin with a low glass transition temperature or a curing agent with low reactivity, coating may be performed roll-to-roll, and blocking may occur in winding after drying. Therefore, blocking can be suppressed. Examples of the reactive group include an epoxy group, a hydroxyl group, a carboxyl group, and a methacryl group.

  Commercially available products can be used for the silicone oil having an epoxy group in the molecular structure. For example, “X-22-173BX” (functional group equivalent: 2,500 g / mol) having an amino group at one end, “X— 22-173DX "(functional group equivalent 4,500 g / mol) (the above, Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned, These may be individual or may be combined multiple.

  Commercially available products can be used for the silicone oil having a hydroxyl group in the molecular structure. For example, “X-22-170BX” (functional group equivalent: 20 g / mol), “X-22-170DX” having a hydroxyl group at one end. (Functional group equivalent 12 g / mol), “X-22-176DX” (functional group equivalent 35 g / mol), “X-22-176GX-A” (functional group equivalent 8 g / mol) (Shin-Etsu Chemical Co., Ltd. Etc.), and these may be used alone or in combination.

  Commercially available products can be used as the silicone oil having a carboxyl group in the molecular structure. For example, “X-22-3710” (functional group equivalent 1,450 g / mol) having a carboxyl group at one end (Shin-Etsu Chemical Co., Ltd.) Etc.).

  Commercially available products can be used for the silicone oil having a methacryl group in the molecular structure. For example, “X-22-174ASX” (functional group equivalent 900 g / mol) having a methacryl group at one end, “X-22-” 174BX "(functional group equivalent 2,300 g / mol)," KF-2012 "(functional group equivalent 4,600 g / mol)," X-22-2426 "(functional group equivalent 12,000 g / mol)," X- 22-2475 "(functional group equivalent 420 g / mol), (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

  The reactive dimethyl silicone oil described above is preferably added at a ratio of 0.1 to 80% by mass with respect to the (meth) acrylic resin. If it is less than 0.1% or exceeds 80%, sufficient interlayer adhesion may not be obtained.

  The glass transition temperature Tg of the cured film of the anchor coat layer 2 is preferably 40 ° C. or higher and 150 ° C. or lower. If it is less than 40 ° C., the durability is low, and sufficient interlayer adhesion may not be obtained. Further, at 150 ° C. or higher, the film may crack due to external factors such as bending and pulling, and the barrier property may be lowered.

  The thickness of the anchor coat layer 2 is usually 1 to 10,000 nm, preferably 50 to 100 nm. When the film thickness exceeds 10,000 nm, it is easy to peel from the polymer film substrate 1 due to the internal stress of the film, and when it is less than 1 nm, the film thickness may not be uniform. Moreover, in order to improve the adhesiveness of the coating film to the polymer film substrate 1, the surface of the polymer film substrate 1 may be subjected to chemical treatment, discharge treatment, or the like before coating. Examples of the coating method include, but are not limited to, bar coater, knife coat, die coat, (reverse) gravure coat, micro gravure coat, spray coat, dip coat, and screen printing. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

  As a means for forming the inorganic oxide layer 3, a heat evaporation method using an electron beam, a laser beam, or the like is preferably used among vacuum evaporation methods, and in particular, the electron beam heat evaporation method is used for film formation speed or inorganic oxide evaporation. This is effective in that the temperature can be raised and lowered to the material in a short time.

  As the metal used for the inorganic oxide layer 3, one or more selected from the group of silicon, aluminum, titanium, tin, zinc, indium, and magnesium can be used.

  The thickness of the inorganic oxide layer 3 formed on the surface of the anchor coat layer 2 by the evaporated deposition material is generally desirably in the range of 5 nm to 300 nm, more preferably 10 nm to 150 nm. The value is appropriately selected.

  However, if the thickness of the inorganic oxide layer 3 is less than 5 nm, a uniform film may not be obtained or sufficient barrier performance may not be exhibited. In addition, when the film thickness exceeds 300 nm, the film cannot retain flexibility, and there is a possibility that the film may crack due to external factors such as bending and tension after the film formation.

  The overcoat layer 4 is provided to protect the hard and brittle inorganic oxide layer 3 and prevent the occurrence of cracks due to rubbing or bending, and from a component containing a water-soluble polymer and alkoxysilane or a hydrolysis product thereof. Become. It is formed by applying a coating liquid containing a water-soluble polymer and alkoxysilane or a hydrolysis product thereof onto the inorganic oxide layer 3 and drying it.

  The thickness of the overcoat layer 4 is usually 1 to 6,000 nm, preferably 5 to 600 nm. When the film thickness exceeds 6,000 nm, it is easy to peel from the base film or sheet due to the internal stress of the film, and when it is less than 1 nm, sufficient barrier properties may not be exhibited. Moreover, in order to improve the adhesiveness of the coating film to a film, you may perform a chemical process, an electrical discharge process, etc. on the surface of a base film before coating. As the coating method of the overcoat layer 4, a normal coating method can be used in the same manner as the anchor coat layer 1. A bar coater, a knife coat, a die coat, a gravure coat, a micro gravure coat, a spray coat, a dip coat, a screen print, and the like are exemplified, but not particularly limited. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used.

  As the water-soluble polymer, polyvinyl alcohol resin (PVA), ethylene-vinyl alcohol copolymer resin (EVOH), polyvinyl pyrrolidone resin (PVP), etc. can be used, and these may be used alone or in combination.

  As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used. Examples of the hydrolysis product of alkoxysilane include those prepared by dissolving alkoxysilane in an alcohol such as methanol, adding an aqueous solution of an acid such as hydrochloric acid to the solution, and causing a hydrolysis reaction.

  Moreover, in order to improve adhesiveness with the inorganic oxide layer 3, you may add a silane coupling agent. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and mercapto groups such as 3-mercaptopropyltrimethoxysilane. And those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate, and the like. These silane coupling agents can be used alone or in combination of two or more. Can be used.

  FIG. 2 is a cross-sectional view of a laminated gas barrier film according to an embodiment of the present invention.

  The laminate gas barrier laminate film 8 is obtained by providing a laminate resin layer 7 on both sides of the gas barrier film 5 of FIG.

  Examples of the material of the adhesive layer 6 include polyurethane, polyester urethane, polyester, polycarbonate polyurethane, polyamide, epoxy resin, polyacrylic acid, polymethacrylic acid, polyethyleneimine, ethylene-acrylic acid copolymer, and ethylene-methacrylic acid copolymer. It is possible to use a solvent-free, solvent-based, water-based, or hot-melt type adhesive containing a polymer, polyvinyl acetate, polyolefin, modified polyolefin, polybutadiene, wax, casein, or a mixture thereof as a main component. it can.

  As the coating method of the adhesive layer 6, a normal coating method can be used as in the anchor coat layer 2. A bar coater, a knife coat, a die coat, a gravure coat, a micro gravure coat, a spray coat, a dip coat, a screen print, and the like are exemplified, but not particularly limited. As the drying method, one or a combination of two or more methods of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation can be used. The thickness is determined according to the purpose, but is generally in the range of 15 μm to 200 μm. Note that the laminate resin layer 7 may be provided only on one side of the gas barrier laminated film 5 of FIG. 1 via the adhesive layer 6.

  The material of the laminate resin layer 7 is selected according to its application. For example, when used as a packaging bag for precision electronic parts, a resin layer having heat sealability is preferably used to seal the bag. The For example, polyethylene such as high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene, polypropylene, ethylene-propylene copolymer, polyester, polyamide, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate. Saponified copolymer, polycarbonate, polyacrylonitrile, nitrocellulose, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, these A metal cross-linked product or a biodegradable resin such as a polylactic acid resin can be used.

  In addition, when used as a member of industrial materials, a resin film layer according to application characteristics such as a liquid crystal display element, solar cell, electromagnetic wave shield, touch panel, vacuum heat insulating material, EL substrate, color filter, etc. is used, For example, polyethylene terephthalate, hydrolysis resistant polyethylene terephthalate, polyethylene naphthalate, polyimide, polyether ether ketone, polyether sulfone, polysulfone, polycarbonate, polyamide, polyvinyl alcohol, ethylene-vinyl acetate copolymer, cellulose triacetate, Polyacetal, modified polyphenylene ether, polyetherimide, polyphenylene sulfide, polyvinyl butyral, polyarylate, ethylene-tetrafluoroethylene copolymer, ethylene trifluoride chloride, tetra Tsu ethylene - perfluoroalkyl vinyl ether copolymer may be used vinylidene fluoride, polyvinyl fluoride, long-term available resins at high temperature and high humidity and the like. The thickness of the laminate resin layer 7 is generally in the range of 10 μm to 500 μm.

  For laminating the laminate resin layer 7 and the gas barrier film 5, for example, a dry laminating method, a non-solvent laminating method, or an extrusion laminating method can be used. For example, when the extrusion laminating method is used, the adhesive layer 6 can be omitted.

  Examples of the present invention will be specifically described below.

<Example 1>
<Anchor coat solution>
Reactive dimethyl was added to (meth) acrylic resin having a ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / n-butyl methacrylate (nBMA) in a molar ratio of 13/72/15 (OH value: 66 mgKOH / g). X-22-170BX (Shin-Etsu Chemical Co., Ltd., functional group equivalent: 2,800 mg KOH / g) having a hydroxyl group at one end as a silicone oil was added to the (meth) acrylic resin at 1%, and Takenate D-as an isocyanate resin. A coating liquid prepared by adjusting 110N (Mitsui Chemicals Co., Ltd.) so that the NCO / OH ratio is 1.0 is applied on a 16 μm PET film by a direct gravure method by a roll-to-roll method, and 120 ° C. And dried for 5 seconds to form a film having a thickness of 0.05 μm. The obtained film was cured at 60 ° C. for 2 days to obtain a urethane film.

<Inorganic oxide layer lamination process>
Metallic silicon and silicon dioxide were used as vapor deposition materials and mixed so that the O / Si ratio was 1.5. The metal silicon used was 95% or more of powder having a diameter of 50 μm or less, and silicon dioxide containing 95% of crystal structure and 95% or more of powder having a diameter of 50 μm or less was used. Next, an electron beam emitted from an electron gun was irradiated to the evaporation material by an electron beam heating type vacuum evaporation apparatus to evaporate, thereby forming a silicon oxide film having a thickness of 30 nm on the anchor coat layer.

<Overcoat solution>
(1) Tetraethoxysilane was hydrolyzed with 0.02 mol / L hydrochloric acid.
(2) A 5% aqueous solution of PVA having a saponification degree of 99% and a polymerization degree of 2400 was prepared.
(3) The solution of (1) was added to the solution of (2) at a ratio of SiO ₂ / PVA = 60/40 to obtain an overcoat layer solution. The inorganic oxide layer was coated with a bar coater and dried at 120 ° C. for 2 minutes to form a 0.4 μm overcoat layer.

<Lamination resin layer lamination process to gas barrier laminated film>
Laminate 50 μm thick hydrolysis resistant PET (Toray, X10S) with a 5 g / m ² polyurethane adhesive on both sides of the gas barrier laminate film with the overcoat layer laminated, and laminate A gas barrier laminate film was obtained.

<Example 2>
Example except that X-22-170BX (Shin-Etsu Chemical Co., Ltd., functional group equivalent: 2,800 mgKOH / g) having one hydroxyl group as a reactive dimethyl silicone oil was added to the (meth) acrylic resin in an amount of 5%. In the same manner as in Example 1, a laminated gas barrier film was obtained.

<Example 3>
A laminated gas barrier film was obtained in the same manner as in Example 1, except that X-22-3710 (Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1450 g / mol) having one carboxyl group as the reactive dimethyl silicone oil was used. .

<Example 4>
Implemented except that X-22-2310 (Shin-Etsu Chemical Co., Ltd., functional group equivalent: 1450 g / mol) having one carboxyl group as a reactive dimethyl silicone oil was added to the (meth) acrylic resin at 5%. A laminated gas barrier film was obtained in the same manner as in Example 1.

<Comparative Example 1>
A laminated gas barrier film was obtained in the same manner as in Example 1 except that no reactive dimethyl silicone oil was added.

<Comparative example 2>
Laminate gas barrier in the same manner as in Example 1 except that KF-96L-0.65cs (manufactured by Shin-Etsu Chemical Co., Ltd.) having methyl groups at both ends as non-reactive dimethyl silicone oil was used instead of reactive dimethyl silicone oil. A characteristic film was obtained.

  About the gas-barrier film of the said Examples 1-4 and Comparative Examples 1-2, the water vapor permeability, the interlayer adhesive force, and the glass transition temperature of the cured film were measured and evaluated by the following methods.

<About water vapor transmission rate>
The water vapor permeability of the laminated gas barrier films after vapor deposition in Examples 1 to 4 and Comparative Examples 1 and 2 was measured at 40 ° C. and 90% RH using a water vapor permeability measuring device (MOCON PERMATRAN 3/33) manufactured by Modern Control. Measured in the atmosphere. The measured value of water vapor transmission rate was used as an index of gas barrier properties.

<Interlayer adhesion>
The measurement of the interlayer adhesion force is performed by using a dump gas (treated at 85 ° C. and 85% RH for 1000 hours) and an accelerated weathering tester (XWOM: xenon weatherometer) for the laminated gas barrier laminated film 8 shown in FIG. The interlayer adhesion after the treatment was evaluated. The test piece was cut into a strip with a width of 10 mm, a part of the end was peeled off, and 300 mm / min. By a tensile tester (Instron). T-type peeling was performed at a speed of ◯, and when the interlayer adhesion was 1N or more, ◯ and less than 1N were evaluated as x. In addition, peeling will peel between the overcoat layer 4 and the adhesive bond layer 6, if adhesion between each layer is enough (refer FIG. 2).

<About glass transition temperature>
A glass transition temperature of the cured film was prepared as an anchor coat layer coating solution having a solid content of 20% and dried at 100 ° C. for 2 hours. The dried cured product was sealed in an aluminum container, and the glass transition temperature was measured by DSC (differential scanning calorimetry). The measurement conditions are from -20 ° C to 10 ° C / min. The temperature was raised to 250 ° C. for 5 minutes and then maintained at 270 ° C./min. The temperature was lowered. This condition was carried out for two cycles, and the measurement data for the second cycle was adopted. In addition, measurement was performed while flowing nitrogen gas into the furnace.

  The measurement results are shown in Table 1 below.

<Evaluation>
As shown in Table 1, each of the laminated gas barrier films according to Examples 1 to 4 exhibited good water vapor permeability and adhesion after the durability test. The laminated gas barrier film according to Comparative Example 1 had high adhesion after the durability test. Since the Tg of the cured film was low, the water vapor permeability was high and the barrier property was low. The laminated gas barrier film according to Comparative Example 2 showed good results in water vapor permeability, but because the non-reactive group dimethyl silicone oil was used, the durability of the film was low, and the adhesion after the durability test was low. .

  The present invention has high gas barrier properties against various gases such as water vapor, high temperature and high humidity, interlayer adhesion and productivity in weather resistance, and can be widely applied to fields where barrier / sealing is required.

DESCRIPTION OF SYMBOLS 1 ... Polymer film base material 2 ... Anchor coat layer 3 ... Inorganic oxide layer 4 ... Overcoat layer 5 ... Gas barrier property laminated film 6 ... Adhesive layer 7 ... Laminate resin layer 8 ... Laminate gas barrier property laminated film

Claims (9)

An anchor coat layer made of an inorganic material and an organic material, an inorganic oxide layer, and an overcoat layer made of an organic material containing an organic material or an inorganic material are laminated in this order on at least one surface of the substrate.
The gas barrier film, wherein the anchor coat layer is made of a graft copolymer of (meth) acrylic resin, isocyanate resin, and modified silicone oil.   The gas-barrier film according to claim 1, wherein the modified silicone oil is a reactive dimethyl silicone oil having a reactive group at one end.   The gas barrier film according to claim 2, wherein the reactive group at one end of the reactive dimethyl silicone oil has any one of an epoxy group, a hydroxyl group, a carboxyl group, and a methacryl group.   4. The gas barrier film according to claim 1, wherein a glass transition temperature of the anchor coat layer is 40 ° C. or more and 150 ° C. or less.   The gas barrier film according to any one of claims 1 to 4, wherein the anchor coat layer has a thickness of 1 nm or more and 10,000 nm or less. The gas barrier film according to claim 1, wherein the inorganic oxide layer is made of SiO 2 _X , and X is 1.5 or more and 1.8 or less.   The gas barrier film according to claim 1, wherein the total thickness of the inorganic oxide layer is 10 nm or more and 150 nm or less.   The gas barrier film according to claim 1, wherein the overcoat layer contains a water-soluble polymer and an alkoxysilane or a hydrolysis product thereof.   The gas barrier film according to any one of claims 1 to 8, wherein the overcoat layer has a thickness of 5 nm or more and 600 nm or less.

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