JP2009125965A - Gas barrier film - Google Patents

Abstract

The present invention relates to a gas barrier film which is used as a base material for industrial materials such as packaging for foods and pharmaceuticals, organic EL, solar cells, etc., which require barrier properties related to permeation of oxygen and water vapor. An excellent gas barrier film having high gas barrier properties and excellent productivity is provided.
A gas barrier film formed by sequentially forming a mixed layer containing at least two kinds of binders and a metal layer made of a metal or a metal oxide on a transparent substrate, wherein the two or more kinds of the gas barrier films are formed. A gas barrier film, wherein a difference between a maximum value and a minimum value of each surface tension of the binder is 5 mN / m or more and 50 mN / m or less.
[Selection figure] None

Description

  The present invention relates to a gas barrier film that is used as a substrate for industrial materials such as packaging for foods and pharmaceuticals, organic EL, solar cells and the like that require barrier properties related to the permeation of oxygen and water vapor.

  Conventionally, various types of packaging materials having barrier properties related to permeation of oxygen and water vapor have been developed. Recently, metal oxide films such as silicon oxide and aluminum oxide are formed on a plastic substrate on a nano scale. Many transparent barrier films have been proposed.

  The transparent barrier film as described above is not limited to food packaging in that it has excellent transparency and high barrier properties against water vapor and oxygen, compared to a barrier film using a conventional aluminum foil or the like, This technology is also expected for industrial use.

A gas barrier film using an inorganic compound thin film such as SiO _X has better gas barrier properties and less humidity dependency than those using a gas barrier polymer such as polyvinyl alcohol and ethylene vinyl alcohol copolymer. Higher barrier properties are required for use in industrial materials.

As a gas barrier film that has undergone two or more processing steps, for example, in Patent Document 1, a film obtained by laminating polyvinyl alcohol on a layer using an acrylic-modified urethane resin is used as a gas barrier film. / M ² · day or more and the barrier property is not high.
Further, in Patent Document 2, an inorganic compound is laminated on a coating film hardened with a polyfunctional ultraviolet curable resin to improve the water vapor transmission rate. There is a concern that the gas barrier property of the inorganic compound to be laminated tends to be lowered due to the surface defect, and the gas barrier property may become unstable in production.
JP 2001-001463 A JP 2002-264274 A

  In view of the above problems, the present invention is to provide a gas barrier film that is excellent in transparency, has a high gas barrier property, and is excellent in productivity.

The invention according to claim 1 is a gas barrier film formed by sequentially forming a mixed layer containing at least two kinds of binders and a metal layer made of metal or metal oxide on a transparent substrate,
The difference between the maximum value and the minimum value of each surface tension of the two or more binders is 5 mN / m or more and 50 mN / m or less.
This is a gas barrier film characterized by the above.

  The invention according to claim 2 is the gas barrier film according to claim 1, wherein at least one of the two or more binders contains F atoms or Si atoms.

  According to a third aspect of the present invention, the metal layer is formed using a physical vapor deposition method or a chemical vapor deposition method, and the thickness of the metal layer is 5 nm or more and 1000 nm or less. The gas barrier film according to claim 1 or 2, wherein the gas barrier film is provided.

  Invention of Claim 4 is a gas barrier film in any one of Claims 1-3 whose film thickness of the said mixed layer is 30 nm or more and 10 micrometers or less.

The invention according to claim 5 is further represented by R ¹ (M-OR ² ) (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M is a metal atom) on the metal layer. The gas barrier film according to any one of claims 1 to 4, wherein an overcoat layer containing at least one metal alkoxide is formed.

  Invention of Claim 6 forms the overcoat layer formed by containing resin which has bifunctional or more (meth) acryl group further on the said metal layer, It is characterized by the above-mentioned. 4. The gas barrier film according to any one of 4 above.

  According to the present invention, the difference between the maximum value and the minimum value of each surface tension of two or more kinds of binders used in the mixed layer is set to 5 mN / m or more and 50 mN / m or less, so that high transparency and high gas barrier properties are achieved. A gas barrier film having can be obtained.

  The gas barrier film in the present invention is formed by sequentially forming a mixed layer containing at least two kinds of binders and a metal layer made of metal or metal oxide on a transparent substrate.

  Although the structure of only three layers of a transparent base material, a mixed layer, and a metal layer may be sufficient, you may form another functional film between each film | membrane other than between a mixed layer and a metal layer, or a film | membrane.

  In a gas barrier film having a metal layer, the denseness of the metal layer is important in order to obtain high gas barrier properties. And it is thought that the film which forms a metal layer contributes to the denseness in the formation stage of a metal layer.

  In general, it is known that a binder having a low surface tension moves to the surface in wet coating. In the present invention, the property is applied to a gas barrier film. In other words, by using a mixed layer composed of binders with different surface tensions, binders with different surface tensions are separated in the mixed layer, and the change in surface tension during coating film formation is reduced by the action of low surface tension components. In order to prevent thermal convection, surface flatness is imparted. As a result, the present inventors have found that the metal layer is made denser.

  Here, the difference between the maximum value and the minimum value of the surface tensions of two or more binders needs to be 5 mN / m or more and 50 mN / m or less. If it is less than 5 mN / m, the surface tension of two or more binders is balanced, so that the binders are not separated, the flatness of the mixed layer is deteriorated, and the metal layer may be a dense film. Can not. If it is larger than 50 mN / m, the surface tension of two or more binders is too different, so that the compatibility is poor and the two or more binders are separated too much, causing defective curing.

  When three or more types of binders are used (for example, binders A, B, and C), when the binder is A, B, and C in descending order of surface tension, the difference between the surface tension of binder A and the surface tension of binder C May be 5 mN / m or more and 50 mN / m or less. The difference in surface tension between the binders A and B is not particularly limited. The same applies when there are four or more binders. The blending ratio of the binder having the maximum value of the surface tension and the binder having the minimum value of the surface tension is preferably in the range of 0.01 to 50 when the former is 1 (weight).

  The mixed layer in the present invention is a film provided for densifying the metal layer, and as the binder, a fluorosurfactant, fluororesin, silicone surfactant, silicone resin, acrylate, or the like can be used.

  As the fluorosurfactant used in the present invention, any kind can be used as long as it uses a fluorocarbon chain as a hydrophobic group. Moreover, you may use it, mixing 2 or more types of fluorine-type surfactant.

  Examples of the fluororesin used in the present invention include trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl acrylate, and hepta. Examples thereof include (meth) acrylates containing fluorine atoms such as decafluorodecyl methacrylate. Moreover, you may use it, mixing 2 or more types of fluororesins.

  Examples of the silicone surfactant and silicone resin used in the present invention include amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, alkoxy-modified silicone, polyether-modified silicone, alkyl-modified silicone, fluorine-modified silicone, Polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, polyether-modified acrylic-containing polydimethylsiloxane, silicon-modified polyacrylic, isocyanate-containing polysiloxane, vinyl silane, methacrylic silane, epoxy List silane, mercaptosilane, aminosilane, ureidosilane, isocyanate silane, etc. It can be.

The acrylates used in the present invention are listed below.
As the (meth) acrylate, any compound having at least one reactive acrylic group in the molecule may be used. For example, isobornyl acrylate, ethoxylated phenyl acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, polyethylene glycol diacrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethoxylated polypropylene glycol dimethacrylate, propoxylated ethoxy Bisphenol A diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, et Silylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate, ethoxylated glycerin triacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol Examples thereof include propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate and the like.

  Moreover, urethane (meth) acrylate can also be used after polyfunctional (meth) acrylate. Any urethane (meth) acrylate can be used as long as it has a urethane bond and (meth) acrylate structure in the molecule, and it is generated from diisocyanate, diol and hydroxyl group-containing (meth) acrylate. can do. As the diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, Xylylene diisocyanate and the like can be mentioned. Examples of the diol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl. Ethylene glycol, 1,4-cyclohexanediol, polyethylene oxide diol, polypropylene oxide diol, polytetramethylene oxide diol, bisphenol A Emissions oxide adducts, propylene oxide adducts of bisphenol A, polycaprolactone diol, polyester Gilles, a polycarbonate diol. Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxyethyl acrylate caprolactone modified product. Examples include 2-hydroxyethyl acrylate oligomer, 2-hydroxypropyl acrylate oligomer, pentaerythritol triacrylate, and the like.

  Polyester acrylate can also be used as the polyfunctional acrylate. Examples of the polyester acrylate include those that are easily formed by reacting a polyester polyol with a 2-hydroxy acrylate or 2-hydroxy acrylate monomer.

  Epoxy acrylate can also be used. The epoxy acrylate is an acrylate obtained by opening an epoxy group of an epoxy resin and acrylated with acrylic acid, and one using an aromatic ring or an alicyclic epoxy is more preferably used.

  Moreover, you may use the binder obtained by reaction of a polyol and isocyanate. Examples of the polyol include polyether polyol, polyester polyol, polyester urethane polyol, acrylic polyol, polycaprolactone polyol, and polycarbonate polyol. Examples of the isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hydrogenated products thereof.

  Here, it is preferable that at least one of the two or more binders used in the mixed layer of the present invention contains F atoms or Si atoms. That is, it is preferable that at least one of the binders is any one of a fluorosurfactant, a fluororesin, a silicone surfactant, and a silicone resin. Since binders containing F atoms or Si atoms generally have a low surface tension, they can be uniformly coated on a substrate, and a mixed layer having excellent flatness can be obtained.

When the mixed layer uses an ionizing radiation curable resin, it can be cured by a photocuring reaction. As a light source for forming a cured film, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge tube, or the like can be used. As irradiation conditions, the ultraviolet irradiation amount is usually about 100 to 1500 mJ / cm ² .

Here, in the case of ultraviolet curing, a photopolymerization initiator is required. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.
Further, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as a photosensitizer.

  These binders and photopolymerization initiators can be dissolved in a solvent and solid content can be adjusted to 1 to 80% by weight, more preferably 3 to 60% by weight, and coated on a transparent substrate.

  Solvents include alcohols such as methanol, ethanol, propanol, hexanol and butanol, glycols such as ethylene glycol, propylene glycol and hexylene glycol, hydrocarbons such as hexane, cyclohexane, octane and decane, xylene, toluene and mesitylene. Aromatic hydrocarbons such as cyclohexane, cycloaliphatic hydrocarbons such as cyclohexane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate, ethylene Examples thereof include, but are not limited to, ethers such as glycol monobutyl ether.

  To the mixed layer, fine particles of an inorganic or organic compound can be added to prevent blocking, impart hardness, impart antistatic performance, or adjust the refractive index.

  Inorganic fine particles used in the mixed layer include oxides such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide, and antimony pentoxide, and complex oxides such as antimony-doped tin oxide and phosphorus-doped tin oxide. In addition, calcium carbonate, talc, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and the like can also be used.

  Organic fine particles used in the mixed layer include polymethyl methacrylate resin powder, acrylic-styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene powder, polycarbonate powder, melamine resin powder, polyolefin Resin powder etc. can be mentioned.

  As the coating method of the mixed layer in the present invention, methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, and a die coater can be used.

  The film thickness of the mixed layer in the present invention is preferably 10 nm to 20 μm, and more preferably 30 nm to 10 μm. If the film thickness is less than 10 nm, the surface of the transparent substrate cannot be uniformly covered, and smoothness cannot be imparted to the formed mixed layer surface. On the other hand, when the film thickness is larger than 20 μm, problems such as generation of cracks due to an increase in curing shrinkage and economic problems due to an increase in cost occur, and productivity is lowered. The film thickness here means the film thickness after curing.

  The metal layer in the present invention is a film made of metal or metal oxide and imparting gas barrier properties. The metal layer is preferably formed using physical vapor deposition or chemical vapor deposition and has a thickness of 5 nm to 1000 nm.

  In the present invention, the surface tension of the fine particles of the solvent, photopolymerization initiator, photosensitizer, inorganic or organic compound is not particularly limited.

  In order to obtain a high gas barrier property, the denseness of the metal layer is important. By forming a metal layer using a physical vapor deposition method or a chemical vapor deposition method, it is possible to obtain a metal layer having higher density than other coating methods.

  Examples of the physical vapor deposition method in the present invention include, but are not limited to, a vacuum vapor deposition method, a sputter vapor deposition method, and an ion plating method.

  Examples of the chemical vapor deposition method in the present invention include, but are not limited to, a thermal CVD method, a plasma CVD method, and a photo CVD method.

  Here, in particular, a coating method performed under reduced pressure using a vacuum apparatus is preferable, such as resistance heating vacuum deposition, EB (Electron Beam) heating vacuum deposition, induction heating vacuum deposition, sputtering, and reactivity. A sputtering method, a dual magnetron sputtering method, a plasma chemical vapor deposition method (PECVD method) or the like is preferably used.

  In the items after the above sputtering method, plasma is used, but plasma such as DC (Direct Current) method, RF (Radio Frequency) method, MF (Middle Frequency) method, DC pulse method, RF pulse method, DC + RF superposition method, etc. However, it is not limited to these methods.

In the case of the sputtering method, a negative potential gradient is generated in the target, which is a cathode, and Ar ⁺ ions receive potential energy and collide with the target. Here, even if plasma is generated, sputtering cannot be performed unless a negative self-bias potential is generated. Therefore, MW (Micro Wave) plasma is not suitable for sputtering because self-bias does not occur. However, in the PECVD method, a chemical reaction, deposition, and a process proceed using a gas phase reaction in plasma, so that a film can be generated without self-bias, and thus MW plasma can be used.

  When the thickness of the metal layer is less than 5 nm, it is difficult to control the thickness, and good gas barrier performance cannot be imparted. On the other hand, when the thickness is larger than 1000 nm, the film formation time becomes long and cracks are likely to occur, which is not preferable. Furthermore, the thickness of the metal layer is preferably 10 nm or more and 200 nm or less. The film thickness here means the film thickness after curing.

  As the material for forming the metal layer, aluminum oxide or silicon oxide, a composite oxide of indium and tin, a composite oxide of indium and cerium, a composite oxide of indium and cerium containing tin and titanium / titanium, or the like is used. . Among these, a silicon oxide film is more preferable because it is superior to other metal oxides in terms of transparency and gas barrier properties.

  Examples of the transparent substrate used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, norbornene, polyimide, and the like. A typical film thickness of about 3 μm or more and 300 μm or less is preferable.

  These transparent base materials may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, and a slip agent as necessary. Further, the surface may be modified such as corona treatment, flame treatment, plasma treatment, and easy adhesion treatment.

  In the present invention, an overcoat layer may be provided on the metal layer.

The overcoat layer in the present invention contains at least one metal alkoxide represented by R ¹ (M-OR ² ) (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M is a metal atom). Or a resin containing a resin having a bifunctional or higher functional (meth) acrylic group can be used. As a result, functions such as protection of the metal layer, barrier properties, and printability can be improved.

In one or more types of metal alkoxides represented by R ¹ (M-OR ² ) (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms, M is a metal atom) in the present invention, Si, Ti, Al, Zr, or the like can be used.

R ¹ (Si—OR ² ) in which the metal M is Si includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy. A silane etc. can be mentioned.

Examples of R ¹ (Zr—OR ² ) in which the metal M is Zr include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.

Examples of R ¹ (Ti—OR ² ) in which the metal M is Ti include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium.

Examples of R ¹ (Al—OR ² ) in which the metal M is Al include tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, and tetrabutoxyaluminum.

  The metal alkoxide may be used alone or in combination of two or more.

In the present invention, the overcoat layer containing at least one kind of metal alkoxide represented by R ¹ (M-OR ² ) is mainly formed using a sol-gel method, but is not limited thereto. Absent. The film thickness (cured film thickness) is preferably about 10 nm to 5 μm.

Examples of the resin having a bifunctional or higher (meth) acrylic group used in the overcoat layer in the present invention include polyethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethoxylated polypropylene glycol dimethacrylate, propoxylated ethoxylated bisphenol A diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol di (meth) acrylate Ethoxylated glycerin triacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, ditri Methylolpropane tetraacrylate, dipentaerythritol hexaacrylate, or the like, urethane acrylate, polyester acrylate, or epoxy acrylate can be used, and an appropriate solvent, photopolymerization initiator, or additive can be added.
The coating method may be a wet film forming method or a dry film forming method, and the film thickness (cured film thickness) is preferably about 10 nm to 20 μm.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The performance of the transparent gas barrier film was evaluated according to the following method.
The total light transmittance was measured according to JIS-K7105 using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
The water vapor permeability was measured by a cup method using a method according to JIS-Z0208, and the moisture permeating the film was measured by the change in weight of calcium chloride under the conditions of 40 ° C. and 90 RH%.
The surface tension was measured in a 25 ° C. environment by the Wilhelmy method (plate method) using CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.

<Example 1>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

Trimethylolpropane ethoxytriacrylate TMPEOTA
(Daicel Cytec, surface tension of 34.3 mN / m) 300 parts by weight of organically modified siloxane EFKA3288
(Ciba Specialty Chemicals, surface tension 22.8 mN / m) 0.3 parts by weight Methyl ethyl ketone (Wako Pure Chemical Industries) 700 parts by weight Irgacure 184 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 1000 mJ ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
This gas barrier film had a water vapor transmission rate of 0.45 g / m ² · day and a total light transmittance of 80%.

<Example 2>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

1,6-hexanediol diacrylate (Kyoeisha Chemical 1.6HX-A, surface tension 29.5 mN / m) 50 parts by weight glycerin propoxytriacrylate (Daicel Cytec, surface tension 33.5 mN / m) 250 parts by weight fluorocarbon modified polymer EFKA3600
(Ciba Specialty Chemicals, surface tension 23.4 mN / m) 0.3 parts by weight Methyl isobutyl ketone (Pure Chemical) 700 parts by weight Irgacure 907 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried so as to have a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 400 mJ ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. The vapor deposition conditions are the same as in Example 1.
This gas barrier film had a water vapor transmission rate of 0.6 g / m ² · day and a total light transmittance of 79%.

<Example 3>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

Pentaerythritol triacrylate (Kyoeisha Chemical PE-3A, surface tension 51.6 mN / m) 300 parts by weight fluorocarbon-modified polymer EFKA3600
(Ciba Specialty Chemicals, surface tension 23.4 mN / m) 0.3 parts by weight Methyl isobutyl ketone (Pure Chemical) 700 parts by weight Irgacure 184 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 400 mJ of ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. The vapor deposition conditions are the same as in Example 1.
This gas barrier film had a water vapor transmission rate of 0.55 g / m ² · day and a total light transmittance of 79%.

<Example 4>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

Trimethylolpropane ethoxytriacrylate TMPEOTA
(Daicel Cytec, surface tension 34.3 mN / m) 300 parts by weight polyether-modified silicone SH3746
(Toray Dow Corning, surface tension 21.1 mN / m) 3 parts by weight Toluene (Toyo Ink) 700 parts by weight Irgacure 184 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 400 mJ of ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. The vapor deposition conditions are the same as in Example 1.
On this deposited film

Tetraethoxysilane (KBE04, Shin-Etsu Chemical) 18 parts by weight Methanol (Kanto Chemical) 10 parts by weight Hydrochloric acid (0.1N) (Kanto Chemical) 72 parts by weight

The coating solution obtained by stirring and hydrolyzing was applied by a bar coating method so as to have a cured film thickness of 0.5 μm, and was cured by heating in an oven at 120 ° C. for 5 minutes.
This gas barrier film had a water vapor transmission rate of 0.4 g / m ² · day and a total light transmittance of 83%.

<Example 5>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

Trimethylolpropane ethoxytriacrylate TMPEOTA
(Daicel Cytec, surface tension 34.3 mN / m) 300 parts by weight polyether-modified silicone SH3746
(Toray Dow Corning, surface tension 21.1 mN / m) 0.4 parts by weight Toluene (Toyo Ink) 700 parts by weight Irgacure 184 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 400 mJ of ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. The vapor deposition conditions are the same as in Example 1.
On this deposited film

Trifunctional acrylate PET-30 (Nippon Kayaku) 200 parts by weight isopropyl alcohol (Toyo Ink) 500 parts by weight 4-hydroxy-4-methyl-2-pentanone (Kanto Chemical) 300 parts by weight Irgacure 907 (Ciba Specialty Chemicals) 20 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 0.5 μm by a bar coating method, and an organic layer was formed by irradiating 1000 mJ of ultraviolet rays with a metal halide lamp.
This gas barrier film had a water vapor transmission rate of 0.4 g / m ² · day and a total light transmittance of 83%.

<Comparative Example 1>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

Glycerin propoxy triacrylate (Daicel Cytec, surface tension 33.5 mN / m) 400 parts by weight Methyl isobutyl ketone (Wako Pure Chemical Industries) 600 parts by weight Irgacure 184 (Ciba Specialty Chemicals) The organic layer was formed by applying and drying to a cured film thickness of 2 μm by a bar coating method, and irradiating 400 mJ of ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. The vapor deposition conditions are the same as in Example 1. This gas barrier film had a water vapor transmission rate of 2.5 g / m ² · day and a total light transmittance of 80%.

<Comparative example 2>
Using a 50 μm polyethylene terephthalate film substrate A4100 (Toyobo Co., Ltd.), using an electron beam heating type vacuum deposition device on its easy-bonding surface, the silicon oxide material (SiO, manufactured by Canon Optron) was evaporated by electron beam heating. A SiOx film having a thickness of 50 nm was formed at a pressure of 1.5 × 10 ⁻² Pa during film formation. The vapor deposition conditions are the same as in Example 1.
This gas barrier film had a water vapor transmission rate of 10 g / m ² · day and a total light transmittance of 80%.

<Comparative Example 3>
Using a 50 μm polyethylene terephthalate film substrate A4100 (Toyobo Co., Ltd.), using an electron beam heating type vacuum deposition device on its easy-bonding surface, the silicon oxide material (SiO, manufactured by Canon Optron) was evaporated by electron beam heating. A SiOx film having a thickness of 50 nm was formed at a pressure of 1.5 × 10 ⁻² Pa during film formation. The vapor deposition conditions are the same as in Example 1. On the deposited film

Trimethylolpropane ethoxytriacrylate TMPEOTA
(Daicel Cytec, surface tension 34.3 mN / m) 400 parts by weight fluorocarbon-modified polymer EFKA3600
(Ciba Specialty Chemicals, surface tension 23.4 mN / m) 0.4 parts by weight Ethyl acetate 600 parts by weight Irgacure 907 (Ciba Specialty Chemicals) 20 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 400 mJ of ultraviolet rays with a metal halide lamp.
This gas barrier film had a water vapor transmission rate of 7 g / m ² · day and a total light transmittance of 86%.

<Comparative example 4>
Using 50μm polyethylene terephthalate film base material A4100 (Toyobo), its easy adhesion surface

PEG600 diacrylate EBECRYL11
(Daicel Cytec, surface tension 44.1 mN / m) 300 parts by weight fluorocarbon-modified polymer EFKA3277
(Ciba Specialty Chemicals, surface tension 41.2 mN / m) 0.3 parts by weight Methyl ethyl ketone (Wako Pure Chemical Industries) 700 parts by weight Irgacure 184 (Ciba Specialty Chemicals) 15 parts by weight

The coating solution obtained by stirring and mixing was applied and dried to a cured film thickness of 2 μm by a bar coating method, and an organic layer was formed by irradiating 1000 mJ ultraviolet rays with a metal halide lamp. A silicon oxide material (SiO, manufactured by Canon Optron, Inc.) is evaporated on the organic layer by electron beam heating using an electron beam heating vacuum deposition apparatus, and the pressure during film formation is 1.5 × 10 ^−2. A 50 nm thick SiOx film was formed at Pa. However, the deposition conditions at this time are acceleration voltage: 40 kV and emission current: 0.2 A.
This gas barrier film had a water vapor transmission rate of 2.5 g / m ² · day and a total light transmittance of 80%.

  Comparing Examples and Comparative Examples (Table 1), the film is a film obtained by processing at least twice on a transparent substrate, and two or more binders having a surface tension difference of 5 mN / m to 50 mN / m. Using a mixed paint, the low surface tension component is transferred to the surface before curing, a film to be cured is used, and the gas barrier property is improved while maintaining the transparency of the transparent gas barrier film configured to process the metal layer thereon. It was confirmed.

Claims (6)

A gas barrier film formed by sequentially forming a mixed layer containing at least two kinds of binders and a metal layer made of metal or metal oxide on a transparent substrate,
The difference between the maximum value and the minimum value of each surface tension of the two or more binders is 5 mN / m or more and 50 mN / m or less.
A gas barrier film characterized by that.   2. The gas barrier film according to claim 1, wherein at least one of the two or more binders contains F atoms or Si atoms.   The metal layer is formed using physical vapor deposition or chemical vapor deposition, and the thickness of the metal layer is 5 nm or more and 1000 nm or less. Or the gas barrier film of 2.   The film thickness of the said mixed layer is 30 nm or more and 10 micrometers or less, The gas barrier film in any one of Claims 1-3 characterized by the above-mentioned. The metal layer further contains at least one metal alkoxide represented by R ¹ (M-OR ² ) (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms and M is a metal atom). The gas barrier film according to claim 1, wherein an overcoat layer is formed.   The gas barrier film according to any one of claims 1 to 4, wherein an overcoat layer containing a resin having a bifunctional or higher (meth) acryl group is further formed on the metal layer. .