JP2009202587A - Gas-barrier film excellent in weatherability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a weather-resistant, gas-barrier film which maintains a high peel strength and excellent gas-barrier properties at high temperature and high humidity in an ultraviolet-irradiated environment. <P>SOLUTION: The gas-barrier film has a base film, a weather-resistant coating layer formed on at least one side of the base film, and a thin inorganic film formed on the surface of the coat layer. The weather-resistant coating layer is produced by crosslinking polycaprolactone polyol of a main component and/or a polycarbonate polyol. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a gas barrier film, and more particularly to a gas barrier film having excellent weather resistance.

Conventionally, a gas barrier film having a plastic film as a base material and an inorganic thin film of silicon oxide, aluminum oxide, magnesium oxide or the like formed on the surface thereof is used for packaging articles that require blocking of various gases such as water vapor and oxygen, For example, it is widely used for packaging for preventing the deterioration of food, industrial products, pharmaceuticals, and the like. In addition to packaging applications, these gas barrier films have recently been used in organic materials such as liquid crystal display elements, solar cells, electromagnetic wave shields, touch panels, organic electroluminescence (EL) elements, organic TFTs, organic semiconductor sensors, and organic light emitting devices. Attention has also been focused on new applications such as substrate films and vacuum heat insulating materials used in devices, electronic paper, film capacitors, inorganic EL elements, color filters, and the like. In these applications, more stringent performance is required, and it is necessary to maintain gas barrier properties even in an environment such as high temperature and high humidity or ultraviolet irradiation. Particularly for films for solar cells used outdoors, there is a demand for a gas barrier film that is extremely excellent in weather resistance with little performance degradation due to ultraviolet rays.
The gas barrier film formed by forming such an inorganic thin film is subjected to a surface treatment on the base film in order to suppress degradation of the gas barrier property caused by peeling or chipping of the inorganic thin film from the base film. Adhesion is improved. Examples of surface treatment methods include corona treatment, plasma treatment, coating treatment, etc. Among them, the coating treatment is useful because it can improve the adhesion of the inorganic thin film and also suppress the bleeding out from the base film. It is.
However, the gas barrier film in which the base film is coated to form an inorganic thin film exhibits the weakest strength in the coating layer with respect to weather resistance.

  Conventionally, as a coating treatment on a base film of a gas barrier film, a polyester-isocyanate cross-linking reaction coat (Patent Document 1), an anchor coat containing a chlorine-containing resin (Patent Document 2), and an ultraviolet light blocking agent were used. A coat layer and the like are disclosed. However, the coating of the cross-linked reaction product of polyester and isocyanate is not suitable because the ester group is hydrolyzed under high temperature and high humidity, and the necessary adhesion is remarkably lowered, and the gas barrier property is lowered. In addition, the anchor coat containing a chlorine-containing resin is not preferable in terms of environmental load, and if the saturated polyester is not blended, the gas barrier property is insufficient, and the saturated polyester is hydrolyzed under high temperature and high humidity. was there.

Japanese Patent Publication No. 6-22976 Japanese Patent Laid-Open No. 10-76593

  The present invention relates to a weather-resistant gas barrier film that can maintain high peel strength and excellent gas barrier properties under high temperature and high humidity and in an ultraviolet irradiation environment.

That is, the present invention
(1) A gas barrier film having a base film, a weather-resistant coating layer formed on at least one surface thereof, and an inorganic thin film layer formed on the surface of the coating layer, the weather-resistant coating layer being a main component A gas barrier film obtained by crosslinking polycaprolactone polyol and / or polycarbonate polyol.
(2) The gas barrier film according to (1) above, wherein the weather-resistant coating layer is obtained by crosslinking polycaprolactone polyol and / or polycarbonate polyol with an isocyanate compound and / or an epoxy compound.
(3) The gas barrier film according to the above (1) or (2), wherein the inorganic thin film layer comprises at least two inorganic thin films.
(4) The gas barrier film according to any one of (1) to (3), wherein the base film is a biaxially stretched film containing polyethylene naphthalate.

  According to the present invention, a weather-resistant gas barrier film capable of maintaining high peel strength and excellent gas barrier properties under a high temperature and high humidity or ultraviolet irradiation environment can be obtained.

Hereinafter, the present invention will be described in detail.
[Base film]
The base film of the gas barrier film of the present invention is preferably a thermoplastic polymer film, and any material can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials. Specifically, polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefin, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 66, polyamide such as nylon 12, copolymer nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, polyvinyl butyral, Examples include polyarylate, fluororesin, acrylate resin, and biodegradable resin. Among these, polyesters, polyamides, and polyolefins are preferable from the viewpoints of film properties and cost. Among these, polyethylene terephthalate and polyethylene naphthalate are particularly preferable from the viewpoint of film properties.
The base film is a known additive such as an antistatic agent, a light blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricant, a crosslinking agent, an antiblocking agent, An antioxidant etc. can be contained.

The thermoplastic polymer film as the substrate film is formed by using the above raw materials, but when used as a substrate, it may be unstretched or stretched. Good. Moreover, you may laminate | stack with the other plastic base material.
Such a base film can be produced by a conventionally known method. For example, a raw material resin is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be oriented substantially amorphously. No unstretched film can be produced. Moreover, by using a multilayer die, it is possible to produce a single layer film made of one kind of resin, a multilayer film made of one kind of resin, and a multilayer film made of various kinds of resins.
The unstretched film is subjected to a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A film stretched in at least a uniaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto. Although a draw ratio can be set arbitrarily, it is preferable that 150 degreeC heat shrink rate is 0.01 to 5%, Furthermore, it is preferable that it is 0.01 to 2%.
Among these, from the viewpoint of film properties, a biaxially stretched polyethylene naphthalate film, a polyethylene terephthalate and / or a coextruded biaxially stretched film of polyethylene naphthalate and other plastics are preferable.

The thickness of the base film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on its use from the viewpoint of mechanical strength, flexibility, transparency, etc. as the base material of the gas barrier laminate film of the present invention. A sheet-like material selected in a range and having a large thickness is also included. Moreover, there is no restriction | limiting in particular about the width | variety and length of a film, According to a use, it can select suitably.
Moreover, in order to improve the applicability | paintability of an anchor coating agent to a base film, and adhesiveness, you may perform surface treatments, such as normal chemical treatment and electrical discharge treatment, before application | coating of an anchor coating agent.

[Weather-resistant coating layer]
In the gas barrier film of the present invention, a weather resistant coating layer is used.
As the resin constituting the weather resistant coating layer of the present invention, it is necessary to use polycaprolactone polyol and / or polycarbonate polyol.

As a coating material, polyester polyol is easily hydrolyzed, but polycaprolactone polyol has better water resistance than adipate polyester polyol, and better weather resistance and heat resistance than polyether polyol. Moreover, polycarbonate polyol is excellent in heat resistance, moisture resistance, and weather resistance compared with polyester polyol and polyether polyol. Further, from the viewpoint of gas barrier properties, those obtained by crosslinking the polycaprolactone polyol are preferable.
On the other hand, polycaprolactone polyol and polycarbonate polyol have the disadvantage that the interlayer adhesion is weaker than polyester polyol, but only the adhesion component such as a crosslinking agent that adjusts the degree of surface treatment such as corona treatment of the substrate film is extremely important. It can be improved by contrivances such as thin coating first, increasing the compounding ratio of the crosslinkable compound in the coating material, etc., thereby making the weather resistance of the coating layer more effective.

(Polycaprolactone polyol)
Polycaprolactone polyol is produced by ring-opening polymerization of ε-caprolactone in the presence of a catalyst having the following polyhydric alcohol as an initiator according to a known method.
Examples of polyhydric alcohols that are polymerization initiators for ε-caprolactone include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Polymerization products or copolymerization products obtained by ring-opening polymerization of ethylene oxide, propylene oxide and butylene oxide using diol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polytetramethylene ether glycol and their polyhydric alcohol as initiators Aliphatic polyhydric alcohols such as cyclohexane dimethanol, cyclohexanediol, hydrogenated bisphenol A, and these glycols as initiators for the ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide Or polyhydric alcohols containing a cyclohexyl group such as a copolymerized product; bisphenol A, hydroquinone bis (2-hydroxyethyl ether), p-xylylene glycol, bis (β-hydroxyethyl) terephthalate and these glycols Polyhydric alcohols containing aromatic groups such as polymerization products or copolymerization products with addition of ethylene oxide, propylene oxide and butylene oxide as initiators; and glycols having carboxyl groups such as dimethylolpropionic acid and diphenolic acid Polyhydric alcohols having various functional groups such as glycols having tertiary amines such as N-methyldiethanolamine can also be used.
Examples of commercially available products include “Placcel 200” series manufactured by Daicel Chemical Industries, Ltd., “TONE” manufactured by Union Carbide Corporation, and the like.

(Polycarbonate polyol)
The polycarbonate polyol can be produced by a known method. Examples of the polycarbonate diol include aliphatic diols having 2 to 12 carbon atoms such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol. A polycarbonate diol obtained by polycondensation by allowing diphenyl carbonate or phosgene to act on these mixtures is preferably used.
In terms of compatibility with an organic solvent or a crosslinkable compound, a polyalkylene carbonate polyol having a number average molecular weight of 10,000 or less, preferably 500 to 5,000, and a polyethylene glycol monoalkyl having a number average molecular weight of 5,000 or less. The repeating structural unit obtained by reacting with ether is — [(CH ₂ ) ₃ —OC (O) O] — or — [(CH ₂ ) ₂ C (CH ₃ ) (CH ₂ ) ₂ —OC (O Ether-modified polycarbonate polyols having O)-are desirable. In addition, a number average molecular weight is a polystyrene conversion value of gel permeation chromatography analysis.

Moreover, it is preferable that the terminal hydroxyl group index is 92.5 to 98.5 in that the crosslinking reaction between the polycarbonate polyol and the crosslinkable compound is homogeneously performed (control is performed so as not to partially increase the molecular weight). More preferably, it is 95.0-97.5. When the number of terminal hydroxyl groups is large, a high molecular weight product is likely to be generated in the crosslinking reaction, and when the number of terminal hydroxyl groups is small, the crosslinking reaction is difficult to proceed sufficiently, the molecular weight distribution of the product is widened, and the hydrolysis resistance after crosslinking is insufficient. Prone. The terminal hydroxyl group index is a percentage of the peak area ratio of the polyol with respect to the sum of the peak areas of the monoalcohol and the polyol analyzed by gas chromatography. In the gas chromatography, the temperature was raised from 40 ° C. to 220 ° C. at 10 ° C./min, held for 15 minutes, and analyzed using a flame ionization detector (FID).
Examples of commercially available products include “Nipporan” manufactured by Nippon Polyurethane Industry Co., Ltd., “PCDL” manufactured by Asahi Kasei Chemicals Corporation, “Placcel CD” manufactured by Daicel Chemical Industries, Ltd., and the like.

The crosslinkable compound is not particularly limited as long as it is a compound or polymer containing two or more functional groups that crosslink and cure with the hydroxyl groups of the polycaprolactone polyol and / or polycarbonate polyol. The above can be appropriately selected and used.
For example, the crosslinkable compound is exemplified by a compound or polymer having a phenol group, an epoxy group, a melamine group, an isocyanate group, or a dialdehyde group. A compound or polymer containing an epoxy group, a melamine group or an isocyanate group is preferable from the viewpoint of crosslinking reactivity and pot life, and an isocyanate group and / or an epoxy group are particularly preferable from the viewpoint of pot life control. More preferably, an isocyanate compound is desirable as a two-component reactive coating agent in terms of component reactivity, weather resistance derived therefrom, hardness and flexibility of the coating layer.
In the present invention, the resin constituting the weather-resistant coat layer is preferably a resin obtained by crosslinking polycaprolactone polyol and / or polycarbonate polyol with an isocyanate compound and / or an epoxy compound.

  The polyisocyanate may be a diisocyanate, a dimer thereof (uretdione), a trimer thereof (isocyanurate, a triol adduct, a burette), or a mixture of two or more thereof. For example, as the diisocyanate component, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4 -Diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane, 4,4'-diisocyanate cyclohexyl methane, isophor Down diisocyanate, dimer acid diisocyanate, norbornene diisocyanate. Moreover, xylene diisocyanate (XDI) type, isophorone diisocyanate (IPDI) type, hexamethylene diisocyanate (HDI) type, etc. are preferred in terms of non-yellowing. Moreover, the isocyanurate body and burette body of hexamethylene diisocyanate are good in terms of fastness, gas barrier properties, and weather resistance.

  The epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, Examples include triglycidyl, tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, and bisphenol type epoxy resin.

The amount of the crosslinkable compound used is not particularly limited and can be appropriately determined depending on the type of the crosslinkable compound, etc., but the reaction between the hydroxyl group of the polycaprolactone polyol and / or the polycarbonate polyol and the crosslinkable group of the crosslinkable compound. The group ratio is preferably hydroxyl group: crosslinking group = 1: 1 to 1:20 from the viewpoint of cohesive strength in the layer and interlayer adhesion, and more preferably 1: 1 to 1:10. A crosslinking group ratio in the above range is advantageous in terms of adhesion, high temperature and high humidity resistance, gas barrier properties, blocking resistance, and the like.
Moreover, in order to accelerate the crosslinking reaction, the crosslinking compound may be added with one or more crosslinking catalysts such as salts, inorganic substances, organic substances, acid substances and alkaline substances. For example, when a polyisocyanate compound is used as the crosslinkable compound, the addition of one or more known catalysts such as dibutyltin dilaurate and tertiary amine is exemplified.
Also contains silane coupling agents, titanium coupling agents, light blocking agents, ultraviolet absorbers, stabilizers, lubricants, antiblocking agents, antioxidants, etc., or they are copolymerized with the above resins Things can be used.

  As a method for forming the weather-resistant coating layer, a known coating method is appropriately adopted. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Alternatively, the vapor deposition film may be immersed in a resin solution. After application, the solvent can be evaporated using a known drying method such as hot drying such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying. Moreover, in order to improve water resistance and durability, the crosslinking process by electron beam irradiation can also be performed.

The thickness of the weather resistant coating layer is preferably about 0.005 to 5 μm, and more preferably 0.01 to 1 μm. If the thickness is 5 μm or less, the slipperiness is good, there is almost no peeling from the base film due to the internal stress of the anchor coat layer itself, and if the thickness is 0.005 μm or more, the thickness is uniform. It is possible to keep the thickness.
In addition, since the weather-resistant coating layer having the above contents is formed on the surface of the base film and flattened, the particles forming the inorganic thin film are densely deposited and can be easily formed to have a uniform thickness. Sex can be obtained.

[Inorganic thin film]
As a method for forming the inorganic thin film, any method such as a vapor deposition method and a coating method can be used, but the vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained. This vapor deposition method includes methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of physical vapor deposition include vacuum deposition, ion plating, and sputtering, and chemical vapor deposition includes plasma CVD using plasma and a catalyst that thermally decomposes a material gas using a heated catalyst body. Examples include chemical vapor deposition (Cat-CVD).

  Furthermore, it is preferable that the inorganic thin film is multilayered in that a high gas barrier property can be stably maintained for a long period of time, and it is more preferable to use at least two inorganic thin film layers. In that case, various film forming methods may be combined. For example, a vacuum deposited film / vacuum deposited film, a vacuum deposited film / plasma CVD film, a vacuum deposited film / plasma treatment / vacuum deposited film, a vacuum deposited film / plasma CVD film / vacuum deposited film in this order on the weather-resistant coating layer , Vacuum deposited film / Cat-CVD film / vacuum deposited film, vacuum deposited film / weather-resistant coating / vacuum deposited film, plasma CVD film / vacuum deposited film, plasma CVD film / vacuum deposited film / plasma CVD film, etc. Examples include a thin film configuration. Among them, the multilayer of the vacuum deposition film / plasma CVD film is preferable in terms of good gas barrier properties, adhesion, and productivity.

  Examples of the inorganic substance constituting the inorganic thin film include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrogenated carbon, and the like, or oxides, carbides, nitrides, or a mixture thereof. Diamond-like carbon mainly composed of silicon oxide, aluminum oxide and hydrogenated carbon. In particular, inorganic oxides such as silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide, particularly silicon oxide, are preferable in that high gas barrier properties can be stably maintained.

  The material gas that can be used for chemical vapor deposition is preferably composed of at least one kind of gas. For example, in the formation of a silicon compound thin film, as the second source gas with respect to the first source gas containing silicon, It is preferable to use a rare gas such as ammonia, nitrogen, oxygen, hydrogen or argon. The first source gas containing silicon includes monosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane. Ethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, etc. alone or 2 Can be used in combination. The source gas may be liquid or gas at room temperature, and the liquid source can be vaporized by a source vaporizer and supplied into the apparatus. In the catalytic chemical vapor deposition method, monosilane gas is preferable from the viewpoint of deterioration of the heated catalyst body, reactivity, and reaction rate.

  The thickness of each inorganic thin film is generally about 0.1 to 500 nm, preferably 0.5 to 100 nm, and more preferably 1 to 50 nm. If it is in the said range, sufficient gas-barrier property will be acquired, and it is excellent also in productivity, without generating a crack and peeling in an inorganic thin film.

[Protective layer]
The gas barrier film of the present invention may have a protective layer in order to protect the uppermost layer of the inorganic thin film. As the resin for forming the protective layer, both solvent-based and water-based resins can be used. Specifically, polyester resins, urethane resins, acrylic resins, polyvinyl alcohol resins, ethylene vinyl Alcohol-based resin, vinyl-modified resin, nitrocellulose-based resin, silicon-based resin, isocyanate-based resin, epoxy-based resin, oxazoline group-containing resin, modified styrene-based resin, modified silicon-based resin, alkyl titanate, etc. alone or in combination Can be used in combination. Further, as the protective layer, one or more kinds of inorganic particles selected from silica sol, alumina sol, particulate inorganic filler and layered inorganic filler are mixed with the one or more kinds of resins in order to improve barrier properties, wear properties and slipperiness. Or a layer made of an inorganic particle-containing resin formed by polymerizing the resin raw material in the presence of the inorganic particles.

As the resin for forming the protective layer, the above aqueous resin is preferable from the viewpoint of improving the gas barrier property of the inorganic thin film. Furthermore, vinyl alcohol resin or ethylene vinyl alcohol resin is preferable as the aqueous resin.
Further, as the protective layer, a resin layer formed by applying an aqueous liquid containing polyvinyl alcohol and an ethylene / unsaturated carboxylic acid copolymer can be used.

  The thickness of the protective layer is preferably 0.05 to 10 μm, more preferably 0.1 to 3 μm, from the viewpoints of printability and processability. A known coating method is appropriately adopted as the formation method. For example, any method such as a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray or a coating method using a brush can be used. Moreover, you may immerse a vapor deposition film in the resin liquid for protective layers. After application, moisture can be evaporated using a known drying method such as hot drying such as hot air drying or hot roll drying at a temperature of about 80 to 200 ° C. or infrared drying. Moreover, in order to improve water resistance and durability, the crosslinking process by electron beam irradiation can also be performed.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples. In addition, performance evaluation of the gas barrier film obtained in each example was performed as follows.

<Peel test>
A urethane-based adhesive (mixed with “Takelac A543” and “Takenate A3” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) is applied to the obtained gas barrier film or the inorganic thin film surface of the gas barrier film after the light resistance test, 80 An adhesive resin layer having a thickness of about 10 μm was formed by drying at 1 ° C. for 1 minute, and an unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film-CTP P1146” manufactured by Toyobo Co., Ltd.) was formed on the adhesive resin layer. Lamination was aged at 40 ° C. for 3 days to obtain a laminate.
Next, according to JIS Z1707, the laminate was cut into a strip shape having a width of 15 mm, and part of its end was peeled off, and 100 mm / min was measured with a peel tester (manufactured by Shimadzu Corporation, product name EZ-TEST). T-type peeling was carried out at a speed of and adhesive strength (g / 15 mm) was measured.

<Measurement of water vapor transmission rate>
Various conditions of JIS Z0222 “moisture-proof packaging container moisture permeability test method” and JIS Z0208 “moisture-proof packaging material moisture permeability test method (cup method)” for laminated laminates each using a gas barrier film before and after the light resistance test According to the above, the water vapor transmission rate was measured.
Using two gas barrier films with a moisture permeable area of 7.0 cm x 7.0 cm square, a bag was prepared with about 10 g of anhydrous calcium chloride as a hygroscopic agent and sealed on all sides, and the bag was heated at 40 ° C and 90% relative humidity. The sample was placed in a thermo-hygrostat, and mass measurement (0.1 mg unit) was performed for up to 14 days as a guideline for mass increase to be almost constant at intervals of 72 hours or more, and water vapor permeability was calculated from the following formula.
Water vapor transmission rate (g / m ² / 24h) = (m / s) / t
m: Mass increase in the last two weighing intervals (g)
s; Moisture permeable area (m ² )
t: Time of last two weighing intervals (h) / 24 (h)

In addition, the said peeling test and water-vapor-permeability measurement are the following about each laminated laminate obtained, and after performing the following high-temperature, high-humidity tests (1) or (2) to this, and a gas-barrier film below. The laminate laminate obtained after the light resistance test was performed.
<High temperature and high humidity test>
(1) The obtained laminate laminate was stored at 60 ° C. × 90 RH% for 30 days.
(2) The obtained laminate laminate was stored at 85 ° C. × 85 RH% for 30 days.
<Light resistance test>
With the obtained gas barrier film, the surface of the inorganic thin film is directed to the light source of a weatherometer (WBL 75XS manufactured by Xenon-type Suga Test Instruments), surface irradiation illuminance 60 W / m ² , measurement wavelength 300 to 400 nm, black panel temperature 63 ° C. Irradiation was performed for 200 hours at a relative humidity of 50%.

<Measurement of film thickness of inorganic thin film and weather-resistant coating layer>
The obtained gas barrier film was embedded in a resin, and an ultrathin section was prepared according to the cross-sectional method and observed with a transmission electron microscope.
<Composition analysis of inorganic thin film>
About the inorganic thin film surface of the obtained gas-barrier film, element composition was analyzed using Shimadzu Corporation ESCA-3400.

Example 1
A biaxially stretched polyethylene naphthalate film (made by Teijin DuPont, “Q51C12”) having a thickness of 12 μm was used as the base film, and the following coating solution was applied to the corona-treated surface and dried to a thickness of 0.1 μm. A coat layer was formed.
Next, SiO is evaporated by a high-frequency heating method under a vacuum of 1.33 × 10 ⁻³ Pa (1 × 10 ⁻⁵ Torr) using a vacuum deposition apparatus, and SiOx (x = 1.7) is formed on the coating layer. A gas barrier film having a film thickness of 20 nm was obtained.
“Placcel 205” manufactured by Daicel Chemical Industries, Ltd. as a coating liquid polycaprolactone diol,
“Denacol EX252” manufactured by Nagase ChemteX Corp. was used as the epoxy resin, and the mixture was mixed so that the equivalent ratio of the epoxy group to the hydroxyl group was 1: 2.

Example 2
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Placcel 220” manufactured by Daicel Chemical Industries, Ltd. as polycaprolactone diol
“Sumidule N-3200” manufactured by Sumitomo Bayer Urethane Co., Ltd. was used as the isocyanate resin, and mixing was performed such that the equivalent ratio of isocyanate groups to hydroxyl groups was 1: 1.

Example 3
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Nipporan 982R” manufactured by Nippon Polyurethane Co., Ltd. as polycarbonate diol
, “Coronate L” manufactured by Nippon Polyurethane Co., Ltd. was used as the isocyanate resin, and mixing was performed so that the equivalent ratio of isocyanate groups to hydroxyl groups was 1: 1.

Example 4
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Placcel CD CD210” manufactured by Daicel Chemical Industries, Ltd. is used as the polycarbonate diol, and “Takenate D-170HN” manufactured by Mitsui Chemicals Polyurethanes is used as the isocyanate resin, so that the equivalent ratio of isocyanate groups to hydroxyl groups is 1: 1. Mixed.

Example 5
An aqueous ammonium salt solution of a copolymer of methacrylic acid and butyl methacrylate (mass ratio 25:75) was applied to the inorganic thin film surface of the gas barrier film of Example 2 and dried to form a protective layer having a thickness of 0.3 μm. did.

Example 6
A vacuum of 10.7 Pa (8 × 10 ⁻² Torr) is used on the inorganic thin film surface of the gas barrier film of Example 2 using a plasma CVD apparatus and using tetraethoxysilane as a raw material and oxygen, nitrogen, and argon as reactive gases. Below, 1 kW was applied from a 13.56 MHz high frequency discharge plasma source to form a SiOxNy (x = 1.6, y = 0.2) film and a plasma CVD film having a thin film thickness of 20 nm. Next, a vacuum deposited film was formed on the plasma CVD film surface in the same manner as in Example 1 to obtain a gas barrier film having three inorganic thin films.

Comparative Example 1
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
Using “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd. as the isocyanate compound and “Byron 300” manufactured by Toyobo Co., Ltd. as the saturated polyester, they were mixed at a weight ratio of 1: 1.

Comparative Example 2
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Takelac UA-902” manufactured by Mitsui Chemicals Polyurethane Co., Ltd. is used as the acrylic polyol, and “Cosmonate 80” manufactured by Mitsui Chemicals Polyurethane Co., Ltd. is used as the aromatic isocyanate, and the equivalent ratio of hydroxyl group to isocyanate group becomes 1: 1. Mixed.

Comparative Example 3
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Pesresin A-120” manufactured by Takamatsu Resin Co., Ltd. was used as the polyester resin, and “JDX-6500” manufactured by Johnson Polymer Co., Ltd. was used as the acrylic resin, and the solid content ratio was 1: 1.

Comparative Example 4
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
“Adeka New Ace Y4-5” manufactured by ADEKA Co., Ltd. is used as an adipate-based polyester polyol, and “Sumidule N-3200” manufactured by Sumitomo Bayer Urethane Co., Ltd. is used as an isocyanate resin. The equivalent ratio of hydroxyl groups to isocyanate groups is 1: 2. It mixed so that it might become.

Comparative Example 5
A gas barrier film was obtained in the same manner as in Example 1 except that the coating liquid was changed to the following.
Using “Desmophen 550U” manufactured by Sumitomo Bayer Urethane Co., Ltd. as the polyether polyol and “Sumidule N-3200” manufactured by Sumitomo Bayer Urethane Co., Ltd. as the isocyanate resin, the equivalent ratio of hydroxyl groups to isocyanate groups is 1: 2. Mixed.

About each obtained gas-barrier film, the peeling test before and after the water-vapor-permeation rate before and behind a light resistance test, a high temperature high humidity test, and a light resistance test was done by the said method. The results are shown in Table 3.

  The gas barrier film of the present invention is widely used for packaging of articles that need to block various gases such as water vapor and oxygen, for example, packaging for preventing deterioration of food, industrial supplies, pharmaceuticals, and the like. Besides packaging applications, organic devices such as liquid crystal display elements, organic EL elements, organic TFTs, organic semiconductor sensors, organic light emitting devices, solar cells, electromagnetic wave shields, touch panels, electronic paper, film capacitors, inorganic EL elements, color It can also be suitably used as a transparent conductive sheet or a vacuum heat insulating material used in a filter or the like.

Claims (5)

  A gas barrier film having a base film, a weather-resistant coating layer formed on at least one surface thereof, and an inorganic thin film layer formed on the surface of the coating layer, wherein the weather-resistant coating layer is a main component A gas barrier film obtained by crosslinking caprolactone polyol and / or polycarbonate polyol.   The gas barrier film according to claim 1, wherein the weather resistant coating layer is obtained by crosslinking polycaprolactone polyol and / or polycarbonate polyol with an isocyanate compound and / or an epoxy compound.   The gas barrier film according to claim 1 or 2, wherein the inorganic thin film layer comprises an inorganic oxide.   The gas barrier film according to any one of claims 1 to 3, wherein the inorganic thin film layer comprises at least two inorganic thin films.   The gas barrier film according to any one of claims 1 to 4, wherein the base film is a biaxially stretched film containing polyethylene naphthalate.