JP2017144603A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which has high gas barrier properties and has high interlayer adhesion even under high temperature and high humidity or after a weathering test.SOLUTION: A gas barrier film 5 is formed by laminating an anchor coat layer 2, an inorganic oxide layer 3, and an overcoat layer 4 in this order on at least one surface of a substrate 1. The anchor coat layer comprises a urethane resin in which an acrylic-styrene copolymer and an isocyanate compound are bonded, the acrylic-styrene copolymer being obtained by copolymerizing an acrylic monomer having a hydroxyl group or a carboxyl group and a styrene monomer.SELECTED DRAWING: Figure 1

Description

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

  Gas barrier films block oxygen and water vapor in precision electronic components such as hard disks and semiconductor modules, backsheets for solar cells, electronic components such as organic EL and electronic paper, packaging fields such as food and pharmaceuticals, and non-packaging fields It is widely used for members that need to be used.

  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. Particularly in food packaging, it is necessary to suppress the oxidation and alteration of proteins, fats and oils, and to maintain the taste and freshness. In addition, the gas barrier film is expected to have applications such as imparting barrier properties and flexibility to elements such as organic EL and electronic paper. Furthermore, in pharmaceuticals that require handling under aseptic conditions, it is necessary to suppress the alteration of active ingredients and maintain their efficacy.

  Therefore, metal foils such as aluminum and aluminum vapor deposited films that have not been affected by temperature, humidity, etc., or polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile ( PAN) and the like, and plastic films laminated or coated with these resins have been used favorably.

  However, a gas barrier resin film or a film coated with a gas barrier resin has a large temperature dependency and cannot maintain a high gas barrier property at high temperatures. Furthermore, PVDC, PAN, etc. after use have the possibility of causing harmful substances when discarded or incinerated.

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

  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 insufficient in terms of high gas barrier properties, high temperature and high humidity (85 ° C., 85% RH), and adhesion strength between layers after a weather resistance test.

  As means for solving the above-mentioned problem, JP-A-2015-51520 arranges an anchor coat layer, an inorganic oxide layer, and an overcoat layer in this order on at least one surface of a polymer film substrate, A gas barrier film is described in which the anchor coat layer is a urethane resin composed of an acrylic resin and an isocyanate resin, and the acrylic resin is block copolymerized using at least one of an acrylate monomer and a methacrylate monomer. ing.

JP2015-51520A

  An object of the present invention is to provide a gas barrier film having high gas barrier properties and high interlayer adhesion even under high temperature and high humidity and after a weather resistance test.

  In the gas barrier film according to the present invention, an anchor coat layer, an inorganic oxide layer, and an overcoat layer are laminated in this order on at least one surface of a substrate, and the anchor coat layer is a hydroxyl group or a carboxyl group. It is characterized by comprising a urethane resin in which an acrylic-styrene copolymer obtained by copolymerizing an acrylic monomer having a group and a styrene monomer and an isocyanate compound are combined.

  According to the present invention, it is possible to provide a gas barrier film having high gas barrier properties and high interlayer adhesion even under high temperature and high humidity and after a weather resistance test.

Sectional drawing of the gas barrier film by one Embodiment of this invention Sectional drawing of the laminated gas barrier film by one Embodiment of this invention

(First embodiment)
Embodiments of the present invention will be described below. FIG. 1 is a cross-sectional view illustrating a gas barrier film according to an embodiment of the present invention. As shown in FIG. 1, the gas barrier film 5 is formed 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. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol , Polycarbonate, polyether sulfone, acrylic, cellulose-based polymer base materials such as triacetyl cellulose, diacetyl cellulose, and the like, 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 resin in which an acrylic-styrene copolymer obtained by copolymerizing an acrylic monomer and a styrene monomer and an isocyanate compound are bonded.

  As an acrylic monomer of the anchor coat layer 2, two or more types selected from (meth) acrylic acid ester monomers and (meth) acrylic acid monomers are used, and one of the two types includes a hydroxyl group or a carboxyl group. (Meth) acrylic acid monomer or acrylic acid monomer having The (meth) acrylic acid ester monomer is not particularly limited, and known ones can be used. For example, methyl acrylate (MA), ethyl acrylate (EA), propyl acrylate (PA), butyl acrylate (BA), cyclohexyl acrylate (CHA), methyl methacrylate (MMA), 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 may be mentioned, but are not particularly limited. Also, the acrylic acid monomer is not particularly limited, and known ones can be used. Examples include acrylic acid (AA) and methacrylic acid (MAA), but are not particularly limited.

  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. Moreover, by using the (meth) acrylic acid ester monomer or (meth) acrylic acid which has a hydroxyl group or a carboxyl group, it reacts with isocyanate, forms a urethane bond, and can improve interlayer adhesion.

  In the present specification, “(meth) acrylic acid” refers to both acrylic acid and methacrylic acid.

  The proportion of the styrene monomer constituting the acrylic-styrene copolymer used in the anchor coat layer 2 (the proportion of structural units derived from the styrene monomer) is preferably 5 mol% or more and 50 mol% or less. If the proportion of the styrene monomer is less than 5 mol%, sufficient interlayer adhesion cannot be obtained after the weather resistance test, and if it exceeds 50 mol%, sufficient interlayer adhesion may not be obtained after the wet heat test.

  The OH value of the acrylic-styrene copolymer is preferably 10 mgKOH / g or more and 150 mgKOH / g. When the OH value is less than 10 mgKOH / g or more than 150 mgKOH / g, sufficient interlayer adhesion may not be obtained after the durability test.

  Examples of the isocyanate compound used for the anchor coat layer 2 include hexamethylene-1,6-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate, 1,3- Various types such as bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Diisocyanates, and various modifications thereof, and dimer bodies, adduct bodies, allophanate bodies, trimer bodies, carbodiimide adduct bodies, biuret bodies, and the like Of the polymer, and polymer obtained by adding a polyhydric alcohol is not particularly limited.

  Moreover, it is preferable that the molar ratio (NCO / OH) of the NCO group of the isocyanate compound to the OH group of the acrylic-styrene copolymer is 0.5 or more and 4.0 or less. If NCO / OH is less than 0.5, sufficient adhesion may not be obtained, and if it exceeds 4.0, barrier properties may be deteriorated due to insufficient curing when applied roll-to-roll.

  The glass transition temperature Tg of the cured film which is a reaction product of the acrylic-styrene copolymer of the anchor coat layer 2 and the isocyanate compound is preferably 40 ° C. or higher and 150 ° C. or lower. When the glass transition temperature Tg of the cured film of the anchor coat layer 2 is less than 40 ° C., the durability is low, and there is a possibility that sufficient interlayer adhesion cannot be obtained. On the other hand, when the glass transition temperature Tg exceeds 150 ° C., the film may be cracked due to external factors such as bending and tension, and the barrier property may be lowered.

In general, the glass transition temperature (Tg) of the polymer copolymer can be obtained as a theoretical calculated value by the following FOX equation (1), and the glass transition temperature (Tg) of the acrylic-styrene copolymer described above is It can be obtained by FOX equation (1).
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ +... + W _n / Tg _n ... Formula (1)
(Wherein, Tg is a glass transition temperature (K), W ₁ , W ₂ ,..., W _n are weight fractions of monomers constituting the urethane resin, and Tg ₁ , Tg ₂ ,. · ·, Tg _n is the glass transition temperature of the homopolymer of each monomer)
However, since the isocyanate compound is not a monomer capable of forming a homopolymer, the glass transition temperature (Tg) of the urethane resin obtained by reacting the acrylic-styrene copolymer and the isocyanate compound described above is obtained by actual measurement.

  The thickness of the anchor coat layer 2 is preferably 10 nm or more and 10,000 nm. If the film thickness is less than 10 nm, the film thickness may not be uniform and sufficient adhesion may not be obtained. Moreover, when exceeding 10,000 nm, there exists a possibility of peeling from the film base material 1 by the internal stress of a film | membrane.

  Moreover, in order to improve the adhesiveness of the coating film to the film base material 1, you may give a chemical process, an electrical discharge process, etc. to the surface of the film base material 1 before coating.

  Examples of the coating method for the anchor coat layer 2 include, but are not limited to, bar coating, knife coating, die coating, (reverse) gravure coating, micro gravure coating, spray coating, dip coating, 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.

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

Among these, the inorganic oxide layer 3 is preferably a vapor deposition film made of silicon oxide (SiO _x ). In this case, it is preferable that X (element ratio O / Si between silicon and oxygen) satisfies 1.5 ≦ X ≦ 1.8. When X is less than 1.5, the transparency of the inorganic oxide layer 3 due to the strong yellow color decreases, and splash occurs during heating with an electron beam when evaporating silicon oxide (SiO _X ). Therefore, it is not preferable. On the other hand, when X exceeds 1.8, the transparency is improved, but there is a problem that the barrier property is lowered.

  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.

  The thickness of the inorganic oxide layer 3 formed on the surface of the anchor coat layer 2 by the evaporated metal 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 film 3 and prevent the occurrence of cracks due to rubbing or bending, and contains a water-soluble polymer and alkoxysilane or a hydrolysis product thereof. Consists of ingredients. The overcoat layer 4 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 10 to 6,000 nm, preferably 50 to 600 nm. If the film thickness is less than 10 nm, sufficient barrier properties may not be exhibited. Moreover, when exceeding 6000 nm, there exists a possibility of peeling from the inorganic oxide layer 3 by the internal stress of a film | membrane. Moreover, in order to improve the adhesiveness of the coating film to the inorganic oxide layer 3, the surface of the inorganic oxide layer 3 may be subjected to chemical treatment, discharge treatment, or the like 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 coat, a knife coat, a die coat, a (reverse) 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. , Those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate, and the like. These silane coupling agents may be used alone or in combination of two or more. Can be used.

(Second Embodiment)
FIG. 2 is a cross-sectional view of a laminated gas barrier film according to an embodiment of the present invention. As shown in FIG. 2, the laminate gas barrier film 8 is obtained by providing a laminate resin layer 7 on both surfaces of the gas barrier film 5 according to the first embodiment described above with an adhesive layer 6 interposed therebetween.

  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 1. A bar coat, 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 can be mentioned, but not particularly limited. As the drying method, a method of applying heat such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, UV irradiation, etc. can be used alone or in combination of two or more. The thickness of the adhesive layer 6 is determined according to the purpose, but is generally in the range of 15 μm to 200 μm.

  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.

  Note that the laminate resin layer 7 bonded via the adhesive layer 6 may be provided only on one side of the gas barrier laminated film 5.

  Examples of the present invention will be specifically described below.

<Example 1>
<Anchor coating layer lamination process>
The ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) / styrene monomer is 12/38/30/20 (OH value: 67 mgKOH / g) in molar ratio so that the molecular weight is 40,000. Copolymerized. Takenate D-110N (manufactured by Mitsui Chemicals, Inc.) as an isocyanate compound was adjusted so that the NCO / OH ratio was 1.0 with respect to the OH group of this (meth) acrylic resin to a solid content of 1%. The coating liquid was applied onto 16 μm PET with a bar coater # 3 and dried at 120 ° C. for 1 minute to form a film with a thickness of 25 nm. The obtained film was cured at 60 ° C. for 2 days to obtain an anchor coat layer which was an acrylic urethane film having a Tg of 85 ° C.

<Inorganic oxide layer lamination process>
The inorganic oxide of the vapor deposition material was metallic silicon and silicon dioxide, which were mixed so that the O / Si ratio was 1.61. 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.

<Lamination process of overcoat layer>
(1) Tetraethoxysilane was hydrolyzed with 0.02 mol / L hydrochloric acid.
(2) A 5 wt% aqueous solution of PVA having a saponification degree of 99% and a polymerization degree of 2300 was prepared.
(3) The solution of (1) was added to the solution of (2) at a ratio of SiO ₂ / PVA = 65/35 to obtain an overcoat layer solution. This solution was coated on the inorganic oxide layer with a bar coater # 5 and dried at 120 ° C. for 2 minutes to form a 300 nm overcoat layer, whereby a gas barrier film having a laminated structure shown in FIG. 1 was obtained. .

<Lamination resin layer lamination process to gas barrier film>
A 50 μm-thick hydrolysis resistant PET (X10S manufactured by Toray, Inc.) was laminated on both sides of the obtained gas barrier film via a 5 g / m ² polyurethane-based adhesive by a dry lamination method, and the lamination shown in FIG. A laminated gas barrier film having a structure was obtained.

<Example 2>
Acrylic urethane film having a Tg of 80 ° C. with a ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) / styrene monomer in a molar ratio of 20/30/30/20 (OH value: 109 mgKOH / g) A gas barrier film and a laminate gas barrier film were obtained in the same manner as in Example 1 except that.

<Example 3>
A gas barrier film and a laminate gas barrier film were obtained in the same manner as in Example 2 except that the NCO / OH ratio was 2.0.

<Example 4>
Example 3 except that the ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / styrene monomer was 12/53/35 (OH value: 64 mgKOH / g) in molar ratio to obtain an acrylic urethane film having a Tg of 105 ° C. In the same manner as above, a gas barrier film and a laminated gas barrier film were obtained.

<Example 5>
A gas barrier film and a laminate gas barrier film were obtained in the same manner as in Example 1 except that the anchor coating forming coating liquid was a 5% solid content coating liquid and an acrylic urethane film having a thickness of 50 nm was obtained.

  Hereinafter, comparative examples of the present invention will be described.

<Comparative Example 1>
Gas barrier properties in the same manner as in Example 1 except that the ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) was changed to 12/58/30 (OH value: 68 mgKOH / g) in molar ratio. A film and a laminate gas barrier film were obtained.

<Comparative example 2>
Gas barrier properties in the same manner as in Example 3, except that the ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) was changed to 25/45/30 (OH value: 136 mgKOH / g) in molar ratio. A film and a laminate gas barrier film were obtained.

<Comparative Example 3>
Gas barrier properties in the same manner as in Example 3, except that the ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) was changed to 12/78/10 (OH value: 66 mgKOH / g) in molar ratio. A film and a laminate gas barrier film were obtained.

<Comparative Example 4>
The ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) is 20/10/70 (OH value: 117 mgKOH / g) in molar ratio, and the NCO / OH ratio is 0.1. Obtained a gas barrier film and a laminated gas barrier film in the same manner as in Example 1.

<Comparative Example 5>
The ratio of hydroxyethyl methacrylate (HEMA) / methyl methacrylate (MMA) / methyl acrylate (MA) is 20/10/70 (OH value: 117 mgKOH / g) in terms of molar ratio, the NCO / OH ratio is 0.1, and the membrane A gas barrier film and a laminate gas barrier film were obtained in the same manner as in Example 1 except that the thickness was 2 μm.

  About the gas-barrier film of the said Examples 1-5 and Comparative Examples 1-5, the water vapor permeability, the measured value of Tg of the cured film of an anchor coat layer, and interlayer adhesive force were measured and evaluated by the following methods.

<About water vapor permeability>
The water vapor permeability of the gas barrier films of Examples 1 to 5 and Comparative Examples 1 to 5 was measured in an atmosphere of 40 ° C. and 90% RH using a water vapor permeability measuring device (MOCON PERMATRAN 3/33) manufactured by Modern Control. did.

<Measured value of Tg of cured film>
The measured value of Tg of the cured film of the anchor coat layer was 10 ° C./min. From −20 ° C. to 250 ° C. using a differential scanning calorimeter (EXSTA6000) manufactured by SII. At 270 ° C./min. At -20 ° C. This was repeated for 2 cycles, and the value for the second cycle was adopted.

<Interlayer adhesion>
Interlayer adhesion was evaluated using the above-described laminated gas barrier film (FIG. 2). Specifically, the laminated gas barrier film was treated with a heat and humidity resistance test at 85 ° C. and 85% RH (PR-4J manufactured by ESPEC Corporation) for 1000 hours, and a weather resistance test apparatus (Atlas manufactured by Toyo Seiki Seisakusho Co., Ltd.). -Interlayer adhesion force after carrying out treatment for 500 hours with a weatherometer (Ci4000) was evaluated. The weather resistance test conditions were a black standard temperature of 65 ° C., a test bath temperature of 40 ° C., a relative humidity of 50% RH, an irradiance of 60 W / m ² , and watering. The test piece was cut into a strip of 10 mm width, part of the end was peeled off, and the tensile tester (AGS-500NX manufactured by Shimadzu Corporation) was used for 4 conditions, that is, 300 mm / min. T-type peeling, 180-degree peeling at a speed of T, and T-type peeling, 180-degree peeling with water attached to the interface. ◯: 3 for Δ, 2 or less for x

  The measurement results are shown in Table 1 below.

<Evaluation>
As shown in Table 1, Examples 1 to 5 showed good results in any of water vapor permeability, interlayer adhesion after the moist heat resistance test, and interlayer adhesion after the weather resistance test. Comparative Examples 1 to 3 showed good results in water vapor permeability and interlayer adhesion after the moist heat test, but the interlayer adhesion after the weather resistance test was low. In Comparative Examples 4 to 5, the water vapor permeability was high, and the interlayer adhesion after the wet heat resistance test and the interlayer adhesion after the weather resistance test were lowered.

  INDUSTRIAL APPLICABILITY The present invention can be used as a gas barrier film excellent in high gas barrier properties against various gases such as water vapor and interlayer adhesion under high temperature and high humidity and after a weather resistance test, and is widely used in fields where gas barrier properties and sealing are required. Applicable.

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

Claims (10)

An anchor coat layer, an inorganic oxide layer, and an overcoat layer are laminated in this order on at least one surface of the substrate.
The gas barrier, wherein the anchor coat layer is made of a urethane resin in which an acryl-styrene copolymer obtained by copolymerizing an acrylic monomer having a hydroxyl group or a carboxyl group and a styrene monomer and an isocyanate compound are combined. Sex film.   The gas barrier film according to claim 1, wherein a ratio of the styrene monomer in the acrylic-styrene copolymer is 5 mol% or more and 50 mol% or less.   The gas barrier film according to claim 1 or 2, wherein the acrylic-styrene copolymer has an OH value of 10 mgKOH / g or more and 150 mgKOH / g or less.   The molar ratio (NCO / OH) of the NCO group of the isocyanate compound to the OH group of the acrylic-styrene copolymer is 0.5 or more and 4.0 or less, any one of claims 1 to 3 A gas barrier film according to claim 1.   5. The gas barrier according to claim 1, wherein a glass transition temperature Tg of a urethane resin in which the acrylic-styrene copolymer and the isocyanate compound are bonded is 40 ° C. or higher and 150 ° C. or lower. Sex film.   The gas barrier film according to claim 1, wherein the anchor coat layer has a thickness of 10 nm to 10,000 nm. The inorganic oxide layer is a vapor deposition film of silicon oxide represented by SiO _X, characterized in that it is a 1.5 ≦ X ≦ 1.8, according to claim 1 Gas barrier film.   The film thickness of the said inorganic oxide layer is 10 nm or more and 150 nm or less, The gas barrier film in any one of Claims 1-7 characterized by the above-mentioned.   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 claim 1, wherein the overcoat layer has a thickness of 50 nm to 600 nm.

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