JP5119312B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film excellent in gas barrier properties and flexibility against oxygen, water vapor and the like.

  Gas barrier films are used in food and pharmaceutical packaging bags in order to prevent the influence of oxygen, water vapor, and the like that cause the quality of contents to change. In addition, the gas barrier film is used to prevent the performance of elements used in solar cell modules, liquid crystal display panels, organic EL (electroluminescence) display panels, etc. from touching oxygen or water vapor. It is also used as a part or as a packaging material for these elements.

  As such a gas barrier film, a synthetic resin film such as a polyvinyl alcohol film or an ethylene-vinyl alcohol copolymer film is used, but the water vapor barrier property is insufficient, and the oxygen barrier property under high humidity conditions. Has the problem of lowering.

  In order to solve the above problem, a gas barrier film formed by forming a metal oxide thin film on a synthetic resin film is known. For example, Patent Document 1 proposes a gas barrier film composed of a three-layer laminate of a hydrolysis-resistant resin film, a metal oxide-coated resin film, and a white resin film.

Japanese Patent Laid-Open No. 2002-100788

  In recent years, solar cell modules, liquid crystal display panels, and organic EL display panels have been desired to have flexibility, and therefore gas barrier films should also have flexibility. ing. However, in the conventional gas barrier film, the metal oxide thin film does not have sufficient flexibility, and if the gas barrier film is bent, the metal oxide thin film is cracked, leading to a decrease in gas barrier properties. there were.

  Then, an object of this invention is to provide the gas barrier film excellent in gas barrier property and flexibility.

  The gas barrier film of the present invention is characterized in that a gas barrier layer containing zinc and tin oxynitrides is laminated and integrated on one surface of a transparent film.

  A gas barrier layer containing zinc and tin oxynitrides is excellent not only in gas barrier properties but also in flexibility. Therefore, the gas barrier film of the present invention using such a gas barrier layer is excellent in both gas barrier properties and flexibility, and can be installed in a state along a curved surface, a liquid crystal display panel An organic EL display panel or the like can be provided.

Sectional drawing of the gas barrier film which is one Embodiment of this invention is shown. Sectional drawing of the gas-barrier film which is other one Embodiment of this invention is shown.

  The gas barrier film of the present invention has a transparent film and a gas barrier layer that is laminated and integrated on one surface of the transparent film.

(Transparent film)
As the resin constituting the transparent film used in the gas barrier film of the present invention, a transparent synthetic resin is used. For example, polyolefin resins such as polyethylene and polypropylene, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, etc. Polyvinyl resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, etc .; Polyether resins such as polyoxymethylene; Nylon-6, Nylon-6 Polyamide resin such as Polyamide, Polyether, Polyimide, Polyetherimide, Polyethersulfone, Polysulfone, Polyetheretherketone, Polyetherketoneketone, etc. Kill. Moreover, these synthetic resins may be used independently and can also use 2 or more types together.

  The transparent film may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant as necessary. The thickness of the transparent film is preferably 3 to 300 μm, more preferably 12 to 300 μm, and particularly preferably 50 to 200 μm.

  The total light transmittance of the transparent film is preferably 80% or more, and more preferably 90 to 100%. A transparent film having a total light transmittance of 80% or more is excellent in transparency. According to the gas barrier film having such a transparent film, a liquid crystal display panel and an organic EL display excellent in image visibility. A panel and a solar cell module with high power generation efficiency can be provided.

  In addition, the total light transmittance of a transparent film can be measured, for example using a haze meter (Nippon Denshoku Industries Co., Ltd. product name NDH2000) by the method based on JISK7105, for example.

(Smoothing layer)
It is preferable that a smoothing layer having excellent surface smoothness is laminated and integrated on one surface of the transparent film. When the transparent film has a convex part that is difficult to cover with a gas barrier layer on one side, when the gas barrier layer is formed on one side of such a transparent film, the tip of the convex part that the transparent film has from the surface of the gas barrier layer May be exposed without being covered with the gas barrier layer, and the gas barrier property of the resulting gas barrier film may be reduced. However, the convex portion of the transparent film preferably covers the entire surface, and the smoothing layer having excellent surface smoothness is laminated and integrated on one surface of the transparent film, so that the convex portion of the transparent film is removed from the surface of the gas barrier layer. Protruding can be suppressed, and a gas barrier film with better gas barrier properties can be provided.

The maximum roughness _Ry of one surface of the smoothing layer on which the gas barrier layer is laminated and integrated is preferably 100 nm or less, more preferably 0.1 to 100 nm, particularly preferably 0.1 to 50 nm, and 0.1 to 15 nm. Most preferred. If the maximum roughness _Ry of one surface of the smoothing layer is too large, either a transparent film or a smoothing layer is produced when a gas barrier layer is formed on one surface of the smoothing layer by a physical vapor deposition method such as sputtering. Alternatively, due to the unevenness on both sides, there is a convex portion that is difficult to cover with the zinc and tin oxynitrides on the surface where the gas barrier layer is laminated and integrated, and the tip portion of this convex portion is not covered with the gas barrier layer, and the gas barrier layer There exists a possibility that it may protrude from the layer surface and the gas barrier property of a gas barrier film may be reduced.

The surface roughness R _a of one surface of the smoothing layer gas barrier layer is laminated and integrated is preferably 0.1 to 100 nm, more preferably from 0.1 to 50 nm, 0.1～15Nm is particularly preferred. The smoothing layer having _a surface roughness Ra on the surface on which the gas barrier layer is laminated and integrated within the above range is easy to be completely covered with the gas barrier layer and has excellent adhesion to the gas barrier layer, Therefore, a gas barrier film having excellent gas barrier properties can be provided.

In the present invention, the maximum roughness R _y and surface roughness R _a in the plane the gas barrier layer of the transparent film is laminated and integrated can be measured by a method based on JIS B0601 (1982 years). For example, using a non-contact three-dimensional micro surface shape measuring system (product name RST-Plus manufactured by Wyco), in accordance with JIS B0601 (1982), any surface on the surface where the gas barrier layer of the smoothing layer is laminated and integrated 5 points, measured measured as the length 1 [mu] m, the arithmetic mean of the obtained measurement values is obtained as a maximum roughness R _y and surface roughness R _a in the plane the gas barrier layer of the transparent film is laminated and integrated be able to.

It has a maximum roughness R _y and surface roughness R _a in the range described above, to form a smoothing layer having excellent surface smoothness can form a coating film having a smooth surface, of a transparent film This can be done using a material that does not reduce transparency. Examples of such a smoothing layer include (1) a transparent synthetic resin coating layer, (2) a layer formed by a sol-gel method using a composition containing a metal alkoxide, and (3) a radical polymerizable group. And a layer formed by curing a composition containing alkoxysilane (A) having a radical, alkoxysilane (B) having no radical polymerizable group, and water.

  (1) The transparent synthetic resin coating layer can be formed by a method in which a composition obtained by dispersing or dissolving a transparent synthetic resin in a solvent is applied to one surface of a transparent film. Preferred examples of the transparent synthetic resin include acrylic resins, methacrylic resins, and epoxy resins. Examples of the solvent include toluene, ethyl acetate, ethanol and the like. Moreover, as for content of the transparent synthetic resin in a composition, 10 to 40 weight% is preferable.

  After applying the above composition to one side of the transparent film, the applied composition is heated, for example, by removing the solvent contained in the applied composition, so that a transparent synthetic resin is provided on one side of the transparent film. The coating layer can be prepared.

  (2) A layer formed by a sol-gel method using a composition containing a metal alkoxide is formed by applying a composition containing a metal alkoxide such as tetramethoxysilane, and a curing catalyst and a solvent as necessary to one surface of the transparent film. Then, after hydrolyzing and dehydrating and condensing the metal alkoxide to form a sol, the coated composition can be heated to remove the moisture and sinter the resulting gel.

  (3) A layer formed by curing a composition containing an alkoxysilane (A) having a radical polymerizable group, an alkoxysilane (B) not having a radical polymerizable group, and water is formed on one surface of the transparent film by radical polymerization. After applying a composition containing an alkoxysilane (A) having a group, an alkoxysilane (B) not having a radical polymerizable group, and water, the applied composition is irradiated with active energy rays to thereby obtain the alkoxysilane. Hydrolysis and dehydration condensation reaction of the alkoxy group of the radical polymer obtained by the radical polymerization and the alkoxy group of the alkoxysilane (B) after the radical polymerization of (A) or while performing the radical polymerization It can produce by the method to make.

  The layer formed by curing a composition containing an alkoxysilane (A) having a radical polymerizable group, an alkoxysilane (B) not having a radical polymerizable group, and water is formed by the method described above. In such a layer, not only a radical polymer of alkoxysilane (A) is formed, but also a dehydration condensate of alkoxysilane (B) is formed so as to crosslink the main chain of the radical polymer. Therefore, it has a dense network structure. Such a layer having a dense network structure not only has excellent surface smoothness, but also can highly prevent the permeation of gases such as oxygen and water vapor.

  In the present invention, the radical polymerizable group means a group capable of addition polymerization by radical polymerization. Examples of such radically polymerizable groups include groups having an unsaturated double bond, and specifically include allyl groups, isopropenyl groups, maleoyl groups, styryl groups, vinylbenzyl groups, (meth) Examples include an acryloxy group, a (meth) acryloxyalkyl group, and a vinyl group. In addition, (meth) acryloxy means acryloxy or methacryloxy.

  Preferred examples of the radical polymerizable group possessed by the alkoxysilane (A) include a (meth) acryloxy group, a (meth) acryloxyalkyl group, and a vinyl group. Alkoxysilane (A) having (meth) acryloxy group or vinyl group is excellent in radical polymerization reactivity and can be highly polymerized, thus forming a dense network structure and forming a smoothing layer with excellent gas barrier properties. can do. The alkoxysilane (A) preferably has one radical polymerizable group.

（式中、Ｒ¹は炭素数４〜９の（メタ）アクリロキシアルキル基、又はビニル基を表し、Ｒ²はアルコキシ基で置換されていてもよい炭素数１〜８のアルキル基を表し、Ｒ³は炭素数１〜４のアルキル基を表し、且つｎは０又は１である。） Preferred examples of the alkoxysilane (A) having a radical polymerizable group include alkoxysilanes represented by the following general formula (I).

(In the formula, R ¹ represents a (meth) acryloxyalkyl group having 4 to 9 carbon atoms or a vinyl group, R ² represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, R ³ represents an alkyl group having 1 to 4 carbon atoms, and n is 0 or 1.)

In R ¹ of the above general formula (I), as the (meth) acryloxyalkyl group having 4 to 9 carbon atoms, a (meth) acryloxymethyl group, a 2- (meth) acryloxyethyl group, and a 3- (meth) ) An acryloxypropyl group is preferred.

R ^{2 in the} general formula (I) is an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group and the like. The alkyl group may be substituted with an alkoxy group. As a C1-C8 alkyl group substituted by the alkoxy group, a methoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group etc. are mentioned preferably, for example.

  Specific examples of the alkoxysilane represented by the general formula (I) include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-methacryloxypropyltriethoxy. Silane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyl-tris (2- Methoxyethoxy) silane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, vinyltrimethoxysilane, and vinyltriethoxysilane. These alkoxysilanes (A) may be used individually by 1 type, and may use 2 or more types together. Especially, since it is excellent in radical polymerization reactivity, 3- (meth) acryloxypropyl trimethoxysilane is mentioned preferably.

（式中、Ｒ^４及びＲ^５はそれぞれ炭素数１〜８のアルキル基を表し、ｍは０〜２の整数である。） The alkoxysilane (B) does not have a radical polymerizable group. As such an alkoxysilane (B), an alkoxysilane represented by the following general formula (II) is preferably used.

(In the formula, R ⁴ and R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, and m is an integer of 0 to 2.)

R ⁴ and R ^{5 in} the general formula (II) are each an alkyl group having 1 to 8 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms. Examples of R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group, and a butyl group. m is preferably 0.

  The alkoxysilane (B) represented by the general formula (II) can give a crosslinked structure between the main chains of the polymer obtained by radical polymerization of the alkoxysilane (A), and is an excellent gas barrier for a smoothing layer. It becomes possible to impart sex.

  Among these, as alkoxysilane (B), since a dense cross-linked structure can be uniformly formed between the main chains of the alkoxysilane (A) polymer, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and Tetrabutoxysilane is preferred. These alkoxysilanes (B) may be used individually by 1 type, and may use 2 or more types together.

  As content of the alkoxysilane (B) in a composition, 1-100 weight part is preferable with respect to 100 weight part of alkoxysilane (A), 1-50 weight part is more preferable, and 1-20 weight part is especially preferable. preferable. When there is too little content of the alkoxysilane (B) in a composition, there exists a possibility that sufficient crosslinked structure cannot be formed between the principal chains of the polymer of alkoxysilane (A). Moreover, when there is too much content of the alkoxysilane (B) in a composition, there exists a possibility that the smoothing layer obtained may become white and transparency may fall.

  It is preferable that the composition further contains a polyfunctional (meth) acrylate (C) in addition to the alkoxysilane (A) and the alkoxysilane (B) described above. The polyfunctional (meth) acrylate (C) means a (meth) acrylate having two or more (meth) acryloyl groups in one molecule. Moreover, polyfunctional (meth) acrylate (C) does not contain a silicon atom. When the composition further contains a polyfunctional (meth) acrylate (C), the copolymer is obtained by radical polymerization of alkoxysilane (A) and polyfunctional (meth) acrylate (C) by irradiation with active energy rays. Is formed. By using such a polyfunctional (meth) acrylate (C), a smoothing layer having excellent surface smoothness and gas barrier properties can be formed in a short time. The (meth) acryloyl group means an acryloyl group or a methacryloyl group. Moreover, (meth) acrylate means an acrylate or a methacrylate.

  As polyfunctional (meth) acrylate (C), dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Bifunctional (meth) acrylates such as; trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; tetramethylolmethane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate And tetrafunctional (meth) acrylates such as 6-functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate. These polyfunctional (meth) acrylates (C) may be used alone or in combination of two or more.

  The content of the polyfunctional (meth) acrylate (C) in the composition is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the alkoxysilane (A). Part is particularly preferred. When there is too little content of polyfunctional (meth) acrylate (C) in a composition, there exists a possibility that the effect acquired by using polyfunctional (meth) acrylate (C) may not be enough. Moreover, when there is too much content of polyfunctional (meth) acrylate (C) in a composition, there exists a possibility that the water vapor permeability of the smoothing layer obtained may fall.

  Moreover, a composition contains water other than the alkoxysilane (A) and alkoxysilane (B) which were mentioned above. By containing water, the hydrolysis reaction and dehydration condensation reaction between the alkoxy group of the alkoxysilane (A) radical polymer and the alkoxy group of the alkoxysilane (B) are promoted, and the radical of the alkoxysilane (A). It becomes possible to form a network structure in which alkoxysilane (B) is crosslinked between the main chains of the polymer.

  The content of water in the composition is preferably 0.1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane (A). If the content of water in the composition is too small, excessive time is required to sufficiently advance the hydrolysis reaction and dehydration condensation reaction of the alkoxy group of the alkoxysilane (B), and the production efficiency of the gas barrier film is increased. There is a risk of lowering. Moreover, when there is too much content of the water in a composition, there exists a possibility that the water which exists excessively may inhibit the polymerization reaction of alkoxysilane (A).

  After applying a composition containing alkoxysilane (A), alkoxysilane (B) and water on one surface of the transparent film, the applied composition is irradiated with active energy rays. Examples of active energy rays applied to the composition include ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among them, an electron beam is preferable because it has sufficient energy for radical polymerization of alkoxysilane (A).

  When the applied composition is irradiated with an electron beam, the acceleration voltage of the electron beam is preferably 10 to 100 kV, and more preferably 10 to 50 kV. Moreover, 50-200 kGy is preferable and the irradiation amount of an electron beam has more preferable 100-175 kGy.

  Radiation polymerization of the alkoxysilane (A) contained in the said composition is performed by irradiating an active energy ray to the composition apply | coated to one surface of the transparent film. Moreover, when the said composition contains polyfunctional (meth) acrylate (C), radical polymerization of alkoxysilane (A) and polyfunctional (meth) acrylate (C) is performed by irradiation of the said active energy ray. Do.

  In addition, since the composition contains water, the alkoxy group and / or the alkoxy group of the alkoxysilane (A) radical polymer is substituted with or after the initiation of the radical polymerization of the alkoxysilane (A). Hydrolysis and dehydration condensation reaction between the alkoxy group thus obtained and the alkoxy group contained in the alkoxysilane (B), and hydrolysis and dehydration condensation reaction between the alkoxy groups contained in the alkoxysilane (B) occur. In order to sufficiently perform such hydrolysis and dehydration condensation reaction, after irradiating the composition coated on one side of the transparent film with active energy rays, these are preferably at a temperature of 40 to 150 ° C., more preferably 40 to It is preferable to leave at 120 ° C. in an environment with a relative humidity of preferably 40 to 80%, more preferably 50 to 70%. The standing time is preferably 0.1 to 10 hours, and more preferably 0.5 to 3 hours.

  Examples of the smoothing layer include the above-described layers (1) to (3). Among these, the layer (3) is preferably used because of excellent surface smoothness and gas barrier properties.

The smoothing layer may contain inert particles. It is possible to more easily adjust the maximum roughness R _y and surface roughness R _a of the smoothing layer by using the inert particles. As the inert particles, substances that do not cause a chemical reaction with other materials constituting the smoothing layer are used. For example, inert inorganic particles such as Al ₂ O ₃ particles, SiO ₂ particles, TiO ₂ particles, BaSO ₄ particles, CaCO ₃ particles, talc particles, and kaolin particles, and inert organic particles such as crosslinked polystyrene particles and acrylic particles. Particles. The average particle diameter of the inert particles is preferably 0.01 μm to 1.0 μm.

  The thickness of the smoothing layer is preferably 100 nm to 10 μm, more preferably 200 nm to 5 μm, and particularly preferably 500 nm to 3 μm. The smoothing layer having a thickness of less than 100 nm may not have sufficient surface smoothness. Moreover, in the smoothing layer whose thickness exceeds 10 μm, the rigidity becomes too high, and the flexibility of the gas barrier film may be lowered.

(Gas barrier layer)
The gas barrier layer used in the gas barrier film of the present invention contains zinc and tin oxynitrides. According to zinc and tin oxynitrides, the gas barrier property of the gas barrier layer can be improved by including tin atoms, and appropriate flexibility can be imparted to the gas barrier layer by including zinc atoms. Therefore, a gas barrier film using a gas barrier layer containing zinc and tin oxynitride can maintain excellent gas barrier properties without cracking in the gas barrier layer even if it is bent or rolled. it can.

Oxynitride of zinc and tin, one general formula (1): in ZnSn _a O _b N _c (wherein, a is 0.1 to 2, b is 0.3 to 4, c is 0. 1 to 1.6). According to the zinc and tin oxynitride represented by the general formula (1), it is possible to provide a gas barrier layer excellent in gas barrier properties and flexibility.

A in the above general formula (1) indicates the ratio (atomic ratio) of the number of tin atoms to the number of zinc atoms, and is limited to 0.1 to 2, preferably 0.3 to 1.5, 0.5 ~ 1 is more preferred . In the above general formula (1), if the atomic ratio a of tin atoms is too large, the flexibility of the gas barrier layer may be lowered. Moreover, if the atomic ratio a of tin atoms is too small in the general formula (1), the gas barrier property of the gas barrier layer may be lowered.

B in the above general formula (1) represents the ratio (atomic ratio) of the number of oxygen atoms to the number of zinc atoms, and is limited to 0.3 to 4 , preferably 0.5 to 3, more preferably 1 to 3. Is preferred . If the atomic ratio b of oxygen atoms is too large in the general formula (1), the gas barrier property of the gas barrier layer may be lowered. Further, if the atomic ratio b of oxygen atoms is too small in the general formula (1), the transparency of the gas barrier layer may be lowered.

C is in the above general formula (1) represents a nitrogen atom relative to the number of zinc atoms (atomic ratio) is limited to 0.1 to 1.6, preferably 0.3 to 1. If the atomic ratio c of nitrogen atoms is too large in the general formula (1), the transparency of the gas barrier layer may be lowered. Further, if the atomic ratio c of nitrogen atoms is too small in the general formula (1), the gas barrier property of the gas barrier layer may be lowered.

  The gas barrier layer may contain, for example, aluminum in addition to zinc and tin oxynitride, but preferably comprises only zinc and tin oxynitride.

  The ratio of zinc atom, tin atom, oxygen atom and nitrogen atom in zinc and tin oxynitrides contained in the gas barrier layer is, for example, XPS (X-ray photoelectron) manufactured by VG Scientific Fix, product name ESCALAB-200R, etc. It can be measured using a spectroscopic surface analyzer.

  Specifically, Mg is used for the X-ray anode of the XPS surface analyzer, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement using the XPS surface analyzer, first, a range of binding energies of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected. Next, with respect to all the detected elements except for the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and measurement was performed from the spectrum of each element. The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, processing was performed with the same software, and the content value of each analysis target element (nitrogen, oxygen, zinc, tin, etc.) was determined as an atomic concentration (at%).

  Before performing the quantitative process, a calibrated calibration of each element was performed, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  The thickness of the gas barrier layer is preferably 20 to 600 nm, and more preferably 150 to 400 nm. If the thickness of the gas barrier layer is too thin, sufficient gas barrier properties may not be imparted to the gas barrier film. Also, if the thickness of the gas barrier layer is too thick, the flexibility of the gas barrier layer will decrease, and if the gas barrier film is bent or rolled, the gas barrier layer will crack and the gas barrier property of the gas barrier film will decrease. There is a risk of causing it.

  In the present invention, the thickness of the gas barrier layer and the thickness of the smoothing layer described above are obtained by photographing the cross section of the gas barrier layer and the smoothing layer at a magnification of 10,000 times or more using a scanning electron microscope. From the image, it is possible to measure the thickness of five or more arbitrary locations in the gas barrier layer and the smoothing layer, respectively, and obtain the arithmetic average value thereof.

  In order to produce a gas barrier layer containing zinc and tin oxynitride on one surface of the transparent film, it is preferable to use a physical vapor deposition method. According to the physical vapor deposition method, the atomic ratio of zinc atoms, tin atoms, oxygen atoms and nitrogen atoms contained in the oxynitride contained in the obtained gas barrier layer can be easily adjusted. Examples of such physical vapor deposition include vacuum deposition, ion plating, and sputtering. Among these, sputtering is preferred, and DC magnetron sputtering is more preferred.

  In order to produce a gas barrier layer by DC magnetron sputtering, for example, an alloy of zinc and tin is used as a target, oxygen gas and nitrogen gas are used as decomposition gases, and zinc and tin are formed on one surface of a transparent film by DC magnetron sputtering. A gas barrier layer can be formed by depositing and depositing oxynitride.

  By adjusting the atomic ratio of zinc atoms and tin atoms in the alloy of zinc and tin and the amount of oxygen gas and nitrogen gas introduced, the atomic ratio of zinc atoms, tin atoms, oxygen gas and nitrogen gas in the resulting oxynitride Can be adjusted to a desired range.

When a zinc and tin oxynitride film is formed by the DC magnetron sputtering method, the film forming chamber of the DC magnetron sputtering apparatus is 1.33 × 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, particularly 0 After reducing the pressure to less than or equal to .27 × 10 ⁻⁴ Pa (2.0 × 10 ⁻⁵ Torr), the pressure in the film forming chamber is 6.67 × 10 ⁻² Pa (5.0 × 10 ⁻⁴ Torr) to 1 Introducing an inert gas such as argon gas and a decomposition gas containing oxygen gas and nitrogen gas until .33 Pa (1.0 × 10 ⁻² Torr) is reached, and zinc and tin oxynitrides are formed by DC magnetron sputtering. It is preferable to start the film formation.

(Gas barrier film)
As shown in FIG. 1, the gas barrier film of the present invention has a transparent film 11 and a gas barrier layer 12 laminated and integrated on one surface of the transparent film 11. As described above, the gas barrier layer 12 is laminated and integrated so as to cover the entire surface of the transparent film 11, whereby a gas barrier film having excellent gas barrier properties and flexibility can be provided.

  Further, as shown in FIG. 2, the gas barrier film of the present invention is laminated on one surface of the transparent film 11, the smoothing layer 13 laminated and integrated on one surface of the transparent film 11, and the one surface of the smoothing layer 13. The gas barrier layer 12 may be integrated. As described above, since the smoothing layer 13 that covers the unevenness of the one surface and is excellent in surface smoothness is laminated and integrated on one surface of the transparent film 11, one surface of the transparent film 11 is formed from the surface of the gas barrier layer 12. It is possible to prevent the portion from being exposed without being covered with the gas barrier layer, and to provide a gas barrier film having excellent gas barrier properties.

  Applications for which the gas barrier film of the present invention is used include packaging of articles that require blocking of various gases such as water vapor and oxygen, and packaging for preventing deterioration of food, industrial products, pharmaceuticals, and the like. It is done. In addition to such packaging applications, the gas barrier film of the present invention is such that elements used in solar cell modules, liquid crystal display panels, organic EL (electroluminescence) display panels, etc. are exposed to oxygen and water vapor. Therefore, it can be used as a part of the product structure or as a packaging material for these elements. Especially, it is preferable that the gas barrier film of this invention is used as a back surface side protection sheet or a light-receiving surface side protection sheet of a solar cell module. The back surface side protective sheet and the light receiving surface side protective sheet are used for protecting the power generating element and a sealing resin such as an ethylene-vinyl acetate copolymer in the solar cell module.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
1. Preparation of smoothing layer On one side of a polyethylene naphthalate film (thickness 75 mm, total light transmittance 88%), 100 parts by weight of 3-methacryloxypropyltrimethoxysilane, 16 parts by weight of tetraethoxysilane, 100 of tripropylene glycol diacrylate After applying a smoothing layer forming composition containing 8 parts by weight of water and 8 parts by weight of water with a gravure coater, an electron beam irradiation device (product name EC300 / 165/800 manufactured by ESI Co., Ltd.) is applied to the applied smoothing layer forming composition. ) To form a radical polymer by performing radical polymerization of 3-methacryloxypropyltrimethoxysilane and tripropyleneglycol diacrylate by irradiating an electron beam under conditions of an acceleration voltage of 10 kV and an irradiation dose of 170 kGy, One side of the composition for forming a smoothing layer that has been irradiated with an electron beam By leaving the polyethylene naphthalate film on the surface in an environment of 120 ° C. and 50% relative humidity for 0.5 hours, the methoxy group derived from 3-methacryloxypropyltrimethoxysilane in the radical polymer and tetraethoxysilane A dehydration condensate of tetraethoxysilane that crosslinks between the main chains of the radical polymer by performing a hydrolysis and dehydration condensation reaction with an ethoxy group and a hydrolysis and dehydration condensation reaction between ethoxy groups of tetraethoxysilane. Then, a smoothing layer (thickness 3 μm, maximum roughness R _y 0.9 nm, surface roughness R _a 0.5 nm) obtained by being laminated and integrated over one surface of the polyethylene naphthalate film was obtained.

2. Preparation of Gas Barrier Layer An alloy of 54 wt% zinc and 46 wt% tin (zinc atom) is placed on the cathode installed in the film forming chamber of a DC magnetron sputtering apparatus (product name MPC-1 manufactured by Sekisui Chemical Co., Ltd.) : A target composed of tin atoms (atomic ratio) = 2: 1), and the pressure inside the film forming chamber is reduced to 1.33 × 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, argon gas, A mixed gas of oxygen gas and nitrogen gas (argon gas: oxygen gas: nitrogen gas (molecular ratio) = 50: 45: 5) is set to 0.47 Pa (3.5 × 10 ⁻³ Torr) in the film formation chamber. After being introduced to the end, a power of 1.9 kW is applied to the cathode, and a polyethylene naphthalate film having a smoothing layer is conveyed at a speed of 0.5 m / min so that the smoothing layer becomes a sputtering surface and smoothing is performed. Have layers The polyethylene naphthalate film by passing 4 times in a deposition chamber that, to prepare a gas barrier layer consisting entirely ZnSn _0.5 O ₃ N ₁ on one surface of the smoothing layer (thickness 350 nm). As a result, a gas barrier film in which a polyethylene naphthalate film, a smoothing layer, and a gas barrier layer were laminated and integrated in this order was obtained.

(Example 2)
1. Preparation of smoothing layer On one surface of a polyethylene naphthalate film (thickness 75 mm, total light transmittance 88%), 100 parts by weight of 3-methacryloxypropyltrimethoxysilane, 10 parts by weight of tetraethoxysilane, and tripropylene glycol diacrylate 120 After applying a smoothing layer-forming composition containing 100 parts by weight of water, 10 parts by weight of water and 100 parts by weight of alumina fine particles (average particle size 10 nm) with a gravure coater, the applied smoothing layer-forming composition is irradiated with an electron beam. Radicals of 3-methacryloxypropyltrimethoxysilane and tripropyleneglycol diacrylate by irradiating an electron beam under the conditions of an acceleration voltage of 20 kV and an irradiation dose of 175 kGy using an apparatus (product name EC300 / 165/800 manufactured by ESI) Polymerize to form a radical polymer Thereafter, the polyethylene naphthalate film having the smoothing layer-forming composition irradiated with the electron beam on the entire surface was allowed to stand in an environment of 120 ° C. and 50% relative humidity for 1 hour, thereby producing 3-methacrylic acid in the radical polymer. Hydroxyl and dehydration condensation reaction of methoxy group derived from loxypropyltrimethoxysilane and ethoxy group of tetraethoxysilane, and hydrolysis and dehydration condensation reaction of ethoxy groups of tetraethoxysilane with each other A smoothing layer (thickness 1 μm, maximum roughness R _y 10 nm, surface roughness) is formed by forming a dehydrated condensate of tetraethoxysilane that crosslinks between the main chains of the polyethylene chain, and is laminated and integrated on one surface of the polyethylene naphthalate film. R _a 3 nm) was obtained.

2. Preparation of gas barrier layer 29 wt% zinc and 71 wt% tin alloy (zinc atom) on the cathode installed in the film formation chamber of a DC magnetron sputtering apparatus (product name MPC-1 manufactured by Sekisui Chemical Co., Ltd.) : A tin atom (atomic ratio) = 1.1.35), the pressure inside the film formation chamber is reduced to 1.33 × 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, and argon is added. A gas mixture of gas, oxygen gas, and nitrogen gas (argon gas: oxygen gas: nitrogen gas (molecular ratio) = 50: 47: 3) is set to 0.43 Pa (3.2 × 10 ⁻³ Torr) in the deposition chamber. ) Is applied to the cathode, and a polyethylene naphthalate film having a smoothing layer is conveyed at a speed of 0.3 m / min so that the smoothing layer becomes a sputtering surface. Smoothing By passing four times a polyethylene naphthalate film deposition chamber having to prepare a gas barrier layer consisting of ZnSn _1.35 O ₁ N _0.4 on a surface of the smoothing layer (thickness 500 nm). As a result, a gas barrier film in which a polyethylene naphthalate film, a smoothing layer, and a gas barrier layer were laminated and integrated in this order was obtained.

(Example 3)
1. Preparation of smoothing layer In the same manner as in Example 1, a smoothing layer (thickness 3 μm, maximum roughness R) obtained by laminating and integrating the entire surface of a polyethylene naphthalate film (thickness 75 mm, total light transmittance 88%). _y 0.9 nm, surface roughness R _a 0.5 nm).

2. Production of Gas Barrier Layer An alloy of 74 wt% zinc and 26 wt% tin (zinc atom) is placed on the cathode installed in the film forming chamber of a DC magnetron sputtering apparatus (product name MPC-1 manufactured by Sekisui Chemical Co., Ltd.) : A target composed of tin atoms (atomic ratio) = 5: 1), and the pressure inside the film formation chamber is reduced to 1.33 × 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, argon gas, A mixed gas of oxygen gas and nitrogen gas (argon gas: oxygen gas: nitrogen gas (molecular ratio) = 50: 45: 5) is set to 0.47 Pa (3.5 × 10 ⁻³ Torr) in the film formation chamber. After being introduced to the end, a power of 1.9 kW is applied to the cathode, and a polyethylene naphthalate film having a smoothing layer is conveyed at a speed of 0.4 m / min so that the smoothing layer becomes a sputtering surface and smoothing is performed. Have layers The polyethylene naphthalate film by passing 4 times in a deposition chamber that, to prepare a gas barrier layer consisting entirely ZnSn _0.2 O _0.4 N _0.1 on one surface of the smoothing layer (thickness 350 nm). As a result, a gas barrier film in which a polyethylene naphthalate film, a smoothing layer, and a gas barrier layer were laminated and integrated in this order was obtained.

(Comparative Example 1)
1. Preparation of smoothing layer In the same manner as in Example 1, a smoothing layer (thickness 3 μm, maximum roughness R) obtained by laminating and integrating the entire surface of a polyethylene naphthalate film (thickness 75 mm, total light transmittance 88%). _y 0.9 nm, surface roughness R _a 0.5 nm).

2. Production of Gas Barrier Layer A target made of only tin is attached to the cathode installed in the deposition chamber of a DC magnetron sputtering apparatus (product name MPC-1 manufactured by Sekisui Chemical Co., Ltd.), and the deposition chamber is 1.33 × The pressure is reduced to 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, and a mixed gas of argon gas, oxygen gas, and nitrogen gas (argon gas: oxygen gas: nitrogen gas (molecular ratio)) = 50:45: 5) is introduced until the pressure in the film forming chamber reaches 0.47 Pa (3.5 × 10 ⁻³ Torr), and then power of 1.9 kW is applied to the cathode and smoothed at a speed of 0.5 m / min. By transporting the polyethylene naphthalate film having a layer so that the smoothing layer becomes a sputtering surface, and passing the polyethylene naphthalate film having the smoothing layer into the film formation chamber four times A gas barrier layer consisting of SnO _1.8 N _0.5 (thickness 350 nm) was produced on one surface of the smoothing layer. As a result, a gas barrier film in which a polyethylene naphthalate film, a smoothing layer, and a gas barrier layer were laminated and integrated in this order was obtained.

(Comparative Example 2)
1. Preparation of smoothing layer In the same manner as in Example 1, a smoothing layer (thickness 3 μm, maximum roughness R _y ) laminated and integrated on one surface of a polyethylene naphthalate film (thickness 75 mm, total light transmittance 88%) 0.9 nm, surface roughness R _a 0.5 nm).

2. Preparation of gas barrier layer An alloy of 50 wt% zinc and 50 wt% tin (zinc atom) is placed on the cathode installed in the film formation chamber of a DC magnetron sputtering apparatus (product name MPC-1 manufactured by Sekisui Chemical Co., Ltd.) : A target composed of tin atoms (atomic ratio) = 1: 0.55), the pressure inside the film forming chamber is reduced to 1.33 × 10 ⁻² Pa (1.0 × 10 ⁻⁴ Torr) or less, and argon is added. After introducing a gas and a mixed gas of oxygen gas (argon gas: oxygen gas (molecular ratio) = 50: 50) until the pressure in the deposition chamber becomes 0.53 Pa (4.0 × 10 ⁻³ Torr), A polyethylene naphthalate film having a smoothing layer is conveyed at a rate of 0.5 m / min by applying a power of 1.9 kW to the cathode so that the smoothing layer becomes a sputtering surface. By passing 4 times data rate film deposition chamber, to prepare a gas barrier layer consisting of ZnSn _0.5 O ₃ on a surface of the smoothing layer (thickness 350 nm). As a result, a gas barrier film in which a polyethylene naphthalate film, a smoothing layer, and a gas barrier layer were laminated and integrated in this order was obtained.

(Evaluation)
The water vapor transmission rate and flexibility of the gas barrier film produced above were evaluated according to the following procedures. The results are shown in Table 1.

(Water vapor transmission rate)
The water vapor transmission rate (%) of the gas barrier film was measured at a temperature of 40 ° C. and a relative humidity of 90% using a gas / vapor transmission rate measuring device (GTR Tech Inc., device name GTR-2100) according to a method based on JIS K7129B. The measurement was performed under the following conditions.

(Flexibility)
A gas barrier film is wrapped around a 150 mmφ ABS rod so that the gas barrier layer is on the outside, and after 15 minutes from the completion of winding, the procedure for opening the gas barrier film by unfolding the gas barrier film is one cycle, This cycle was repeated 50 times. Thereafter, a cross-cut test was performed in accordance with JIS K5400. In this cross-cut test, using a single-blade razor on the surface of the gas barrier layer, 11 cuts were made in the vertical and horizontal directions at intervals of 1 mm on the surface of the gas barrier layer to make 100 squares of 1 mm square. The vertical cut and the horizontal cut intersected at an angle of 90 °. A commercially available adhesive tape is pasted on 100 squares, and the adhesive tape is peeled off in the direction perpendicular to the surface of the gas barrier layer with the hand of the tip of the adhesive tape, and smoothed as the adhesive tape is peeled off. The number of squares peeled from the layer was measured, and the flexibility was evaluated according to the following criteria. “A grid is peeled from the smoothing layer” means a state in which an area of 50% or more of each grid is separated from the smoothing layer.
A: No peeling was observed. B: The number of peeled squares was 1 or more and less than 5.
C: The number of squares peeled off was 5 or more and less than 10.
D: The number of squares peeled off was 10 or more.

  The gas barrier film of the present invention is excellent in gas barrier properties and flexibility. Therefore, according to such a gas barrier film, a solar cell module, a liquid crystal display panel, an organic EL display panel, etc. that can be bent or rolled and can be installed along a curved surface are provided. Can be provided.

11 Transparent film 12 Gas barrier layer 13 Smoothing layer

Claims (3)

On one surface of a transparent film, the general formula _{(1): ZnSn a O b} N c ( wherein, a is 0.1 to 2, b is 0.3 to 4, c is 0.1 to 1. 6)), and a gas barrier layer comprising a gas barrier layer containing zinc and tin oxynitrides represented by 6) . On one surface of the transparent film, a general formula (1): ZnSn _a O _b N _c (wherein a is 0.1 to 2, b is 0.3 to 4, c Is a gas barrier layer containing a zinc and tin oxynitride represented by the formula (1 ) to (1.6) . The method for producing a gas barrier film according to claim 2 , wherein the physical vapor deposition method is a sputtering method.

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