JP2013233744A - Gas barrier film and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-barrier laminated film that has superior optical characteristics while having enough gas barrier properties and has superior production stability having no variation in various performances in manufacturing.SOLUTION: A gas barrier film has an inorganic layer formed by a vacuum vapor deposition method at least in one side surface of an base material. The inorganic layer formed by the vacuum vapor deposition is formed by setting up vapor deposition material including silicon and silicon monoxide in a crucible whose inner surface of a housing comprises materials not active to the silicon monoxide gas, and evaporating the vapor deposition material by heating.

Description

  The present invention relates to a gas barrier film mainly used as a packaging material such as food and pharmaceuticals, a packaging material such as an electronic device, electronic paper, and a material for a solar cell, and a method for producing the same.

The gas barrier film is mainly used as a packaging material for foods and pharmaceuticals to prevent the influence of oxygen and water vapor, which cause the quality of the contents to change, and is used as a liquid crystal display panel, EL display panel, electronic paper, An element formed in a solar cell or the like is used as a packaging material such as an electronic device, electronic paper, or a solar cell material in order to avoid performance deterioration due to contact with oxygen or water vapor. In recent years, gas barrier films are sometimes used for reasons such as imparting flexibility and impact resistance to portions where glass has been used conventionally.
In general, such a gas barrier film has a structure in which a gas barrier layer is formed on one or both sides of a plastic film as a base material. And the gas barrier layer is formed in the said gas barrier film by various methods, such as a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method).

Physical vapor deposition (PVD) is a method in which a solid vapor deposition material is vaporized by heat or plasma energy to form a thin film on a substrate. Examples include vacuum vapor deposition, molecular beam epitaxy, ion plating, and sputtering. Can be mentioned.
Among these physical vapor deposition methods, the vacuum vapor deposition method is widely used because it is easy to increase the area and can form a gas barrier layer at low cost. In the vacuum vapor deposition method, a gas barrier layer is formed on a substrate by placing a crucible, a vapor deposition material installed in the crucible, a substrate, a heat source, and the like in a vacuum vessel and vaporizing the vapor deposition material by heating (Patent Document 1). , 2).

JP-A-7-331419 JP 2001-295029 A

However, when an inorganic layer made of SiOx is formed by a general vacuum deposition method such as Patent Documents 1 and 2, the optical performance such as transparency is not sufficient, and the production ends from the production start stage of the long product. There was a problem that the gas barrier properties and optical characteristics gradually decreased over the stages, and the production stability was insufficient.
The problem to be solved by the present invention is a gas barrier laminate film having a sufficient gas barrier property, excellent optical performance, no variation in the performance during production, and excellent production stability, and a method for producing the film It is to provide.

  As a result of diligent research to solve the above problems, the present inventor reacts with graphite, which is a crucible material, in which silicon monoxide gas generated in the process of forming an inorganic layer containing SiOx by a vacuum deposition method is generated by the reaction. It has been found that an impure gas such as carbon monoxide is a cause of impairing the optical performance and production stability of the gas barrier laminated film, and has been solved.

  The present invention has an inorganic layer formed by a vacuum deposition method (hereinafter sometimes referred to as “PVD”) on at least one surface of a substrate, and the inorganic layer formed by the vacuum deposition method (PVD) The inner surface of the storage part is formed by installing a vapor deposition material containing silicon and / or silicon monoxide in a crucible made of a material inert to silicon monoxide gas, and vaporizing the vapor deposition material by heating. It is related with the gas barrier film.

  The present invention also provides an inorganic layer formed by vacuum deposition (PVD), an inorganic layer formed by chemical vapor deposition (hereinafter sometimes referred to as “CVD”), and vacuum deposition on at least one surface of a substrate. (1) One or more inorganic layers formed by the vacuum deposition method (PVD) are made of a material in which the inner surface of the storage portion is inert to silicon monoxide gas. The present invention relates to a gas barrier film, which is formed by installing a vapor deposition material containing silicon and / or silicon monoxide in a crucible and vaporizing the vapor deposition material by heating.

  Further, according to the present invention, a deposition material containing silicon and / or silicon monoxide is placed in a crucible made of a material that is inert to silicon monoxide gas on the inner surface of the storage portion, and the deposition material is vaporized by heating. The present invention relates to a method for producing a gas barrier film, wherein an inorganic layer is formed on at least one surface of a substrate by a vacuum deposition method.

  In the present invention, an inorganic layer formed by vacuum deposition, an inorganic layer formed by chemical vapor deposition, and an inorganic layer formed by vacuum vapor deposition are formed in this order on at least one surface of the substrate. Vacuum deposition in which a deposition material containing silicon and / or silicon monoxide is placed in a crucible made of a material that is inert with respect to silicon monoxide gas, and the deposition material is vaporized by heating. The present invention relates to a method for producing a gas barrier film formed by a method.

  The present invention provides a gas barrier film having a sufficient gas barrier property, excellent optical performance, and good production stability, and a method for producing the film.

Hereinafter, the present invention will be described in detail.
<Gas barrier film A>
The first embodiment of the gas barrier film of the present invention (hereinafter sometimes referred to as “first embodiment”) has an inorganic layer formed by vacuum deposition (PVD) on at least one surface of a substrate. In addition, an inorganic layer formed by the vacuum deposition method (PVD) (hereinafter sometimes referred to as “PVD inorganic layer”) is placed in a crucible whose inner surface of the storage portion is made of a material that is inert to silicon monoxide gas. It is an inorganic layer (hereinafter sometimes referred to as “specific PVD inorganic layer”) formed by installing a vapor deposition material containing silicon and / or silicon monoxide and vaporizing the vapor deposition material.

<Gas barrier film B>
In the second embodiment of the gas barrier film of the present invention (hereinafter sometimes referred to as “second embodiment”), an inorganic layer formed by PVD and an inorganic layer formed by CVD on at least one surface of the substrate. (Hereinafter, sometimes referred to as “CVD inorganic layer”) and an inorganic layer formed by PVD in this order, and one or more inorganic layers formed by the vacuum deposition method are such that the inner surface of the storage portion is silicon monoxide. It is an inorganic layer (specific PVD inorganic layer) formed by installing a vapor deposition material containing silicon and / or silicon monoxide in a crucible made of a material inert to gas and vaporizing the vapor deposition material. is there.

  Hereinafter, unless otherwise specified, the “gas barrier film of the present invention” includes both gas barrier films A (first form) and B (second form).

[Base material]
As a base material of the gas barrier film of the present invention, a substrate made of a plastic film is preferable. The raw material can be used without particular limitation as long as it is a resin that can be used for ordinary packaging materials, electronic paper, and solar cell 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, polyamides such as nylon 12 and copolymer nylon; polyvinyl alcohol, ethylene-vinyl acetate copolymer partial hydrolyzate (EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate, Examples include polyvinyl butyral, polyarylate, fluororesin, acrylic resin, and biodegradable resin. Among these, polyester, polyamide, polyolefin, and biodegradable resin are preferable from the viewpoint of film strength and cost, and polyethylene terephthalate (PET) and polyethylene-2 are preferable from the viewpoint of surface smoothness, film strength, heat resistance, and the like. Polyester such as 1,6-naphthalate (PEN) is particularly preferred.
The resin content in the plastic film is preferably 50 to 100% by mass.
In addition, the base material 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 oxidation agent. An inhibitor or the like can be contained.

  The plastic film as the substrate is formed by using the above raw materials, but when used as the substrate, it may be unstretched or stretched. Further, it may be a single layer or a stacked layer. Such a substrate can be produced by a conventionally known method. For example, the raw material is melted by an extruder, extruded by an annular die or a T die, and rapidly cooled to be substantially amorphous and not oriented. A stretched film can be produced. 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 a uniaxial direction or a biaxial direction can be produced by stretching in a direction (horizontal axis) perpendicular thereto.

  The thickness of the substrate is usually in the range of 5 to 500 μm, preferably 10 to 200 μm, depending on its use from the viewpoint of mechanical strength, flexibility, transparency and the like as the substrate of the gas barrier film of the present invention. Also included are sheets that are selected and have a large thickness. Moreover, there is no restriction | limiting in particular about the width | variety and length of a base material, According to a use, it can select suitably.

[Inorganic layer formed by vacuum vapor deposition (PVD)]
The gas barrier film of the present invention has a PVD inorganic layer on at least one surface of the substrate in the first form, and a PVD inorganic layer and CVD on at least one surface of the substrate in the second form. It has an inorganic layer and a PVD inorganic layer in this order. Here, the PVD inorganic layer of the first form and the PVD inorganic layer of at least one of the second form are specific PVD inorganic layers. In addition, when it has two or more PVD inorganic layers, it is preferable that two or more PVD inorganic layers are specific PVD inorganic layers, and it is more preferable that all are specific PVD inorganic layers.

[Specific PVD inorganic layer]
The specific PVD inorganic layer becomes the inorganic layer of the gas barrier films A and B of the present invention as described above, and has the above-described configuration.
This particular PVD inorganic layer is excellent in optical properties (total light transmittance conforms to JIS K7361-1, L ^* values and b ^* values in the L ^* a ^* b ^* display color system) while having a gas barrier property And production stability can be made favorable. The reason is considered as follows.

First, when a vapor deposition material containing silicon monoxide is vaporized by heating, silicon monoxide gas is generated. This silicon monoxide gas is very reactive, and the following reaction occurs with the graphite member constituting the crucible.
C (s) + SiO (g) → SiC (s) + CO (g)
C (s) + SiO (g) → Si (s) + CO (g)
The carbon monoxide gas generated by the above reaction can not only become an impurity of the PVD inorganic layer, but also reduce the degree of vacuum in the vapor deposition apparatus and cause structural defects in the PVD inorganic layer. As a result, the gas barrier properties and optical properties of the gas barrier film are deteriorated. Also, it is possible to use a plurality of crucibles instead of a single unit depending on the area to be formed and the required performance. In that case, the generation of carbon monoxide gas is particularly increased. In addition, since the above reaction occurs continuously, the frequency of occurrence of defects fluctuates over time even within the same manufacturing process, for example, there is a difference in gas barrier properties and optical characteristics between the manufacturing start stage and the manufacturing end stage, Production stability cannot be improved.
When the deposition material is silicon, the following reaction occurs between the natural oxide film (SiO ₂ ) generated on the surface of the silicon powder and the silicon powder (Si), and silicon monoxide gas is generated. Since the silicon monoxide gas causes a reaction similar to that described above with the graphite member constituting the crucible, the same performance deterioration as described above occurs even when the vapor deposition material is silicon. The same applies to the case where the vapor deposition material is a mixture of silicon and silicon dioxide.
SiO ₂ (s) + Si (s) → 2SiO (g)
On the other hand, in the present invention, since the inner surface of the storage portion uses a crucible made of a material that is inert to silicon monoxide gas, the reaction between the silicon monoxide gas and the crucible is prevented, and sufficient gas barrier properties are obtained. It is excellent in optical characteristics (total light transmittance according to JIS K7361-1, L ^* a ^* b ^* display color system, L ^* value and b ^* value), and production stability can be improved.

  In addition, the specific PVD layer exhibits a remarkable effect when another PVD layer, a CVD layer described later, or a coating layer (a protective layer described later) in the barrier film manufacturing process is laminated on the layer. That is, when another layer is stacked on a PVD layer in which impurities are mixed or a defect is generated, the surface shape of the PVD layer is affected, and a defective portion is also generated in the layer stacked there. In such a case, the problem does not occur, and the gas barrier properties and optical characteristics of the multilayer laminate can be improved.

The basic structure of the crucible includes a storage portion in which the vapor deposition material is installed, and an opening through which the vaporized vapor deposition material is discharged to the deposition object. In the present invention, a crucible made of a material that is inert to the silicon monoxide gas is used for the inner surface of the storage portion, and preferably the entire surface (inner surface and outer surface) of the storage portion is inert to the silicon monoxide gas. Use crucibles made of different materials.
As the crucible, the inner surface or the entire surface of the storage portion made of a base material such as graphite is coated with a material that is inert to silicon monoxide gas, and the inner portion of the storage portion that is the base material is made of an inert material. And a case where the entire crucible is made of the inactive material. From the viewpoint of long-term stability, the entire crucible is preferably made of an inactive material.
Elements related to the shape and size of the crucible such as the shape and volume of the storage portion and the area of the opening can be appropriately selected within a known range in accordance with the size of the non-deposited material.

Inactive materials include metals belonging to Group 4 such as titanium, zirconium and hafnium, metals belonging to Group 5 such as vanadium, niobium and tantalum, metals belonging to Group 6 such as chromium, molybdenum and tungsten, and rhenium. , Refractory metals such as osmium, iridium, ruthenium, rhodium, etc., metal compounds (carbides, nitrides, oxides) of these refractory metals, carbides such as silicon carbide, boron carbide, silicon nitride, boron nitride One or more selected from nitrides such as aluminum nitride can be used. Among these metals and metal compounds, silicon carbide and silicon nitride are preferable from the viewpoints of stability and handleability.
Since the inert material is exposed to a high temperature during vapor deposition, the melting point is preferably 1600 ° C. or higher.

  When the base material is coated with an inert material, the thickness of the coating layer is preferably 10 to 1000 nm. Examples of a method for coating the base material with an inert material include a chemical vapor deposition method. For example, in order to form a silicon carbide film on the surface of a graphite base, a means for uniformly reacting a graphite material and a silicon monoxide gas in a controlled atmosphere, a method of pressurizing and impregnating silicon, a thermal CVD or a plasma CVD method And a method of providing a coating layer. In order to obtain a uniform surface coating, a method of providing a coating by a CVD method is preferable.

The term “inert” as used in the present invention refers to a substance that hardly causes a chemical reaction to silicon monoxide gas. The degree of inertness can be measured by the concentration of carbon monoxide gas in the vapor deposition apparatus. For example, a quadrupole mass spectrometer is provided in a vacuum deposition apparatus, and a specific PVD layer having a thickness of 250 nm is formed on a biaxially stretched polyethylene naphthalate film under a vacuum of 2 × 10 ⁻³ Pa in the vacuum deposition apparatus. The forming step is performed, and the gas partial pressure of mass number 28 is measured before starting the film forming process and during the film forming process. At that time, if the gas partial pressure during the film formation step is twice or less that before the start of the step, it can be said that the inner surface of the crucible used in the step is an inert material.

The vapor deposition material used to form the specific PVD layer is mainly silicon and / or silicon monoxide, but aluminum, magnesium, zinc, tin, nickel, titanium, carbon, their oxides, carbides, nitrides, etc. Other inorganic substances, silicon dioxide, silicon nitride, or the like may be mixed and used. When silicon is used as the vapor deposition material, it is preferably mixed with silicon dioxide.
The specific PVD layer formed from these vapor deposition materials is preferably composed of SiOx. In this case, the range of x is preferably 1.20 to 1.90 in terms of barrier properties, more preferably 1.20 to 1.70, and preferably 1.20 to 1.45. Further preferred.

The shape of the vapor deposition material is preferably one formed by sintering and molding an inorganic powder containing silicon powder and / or silicon monoxide powder having a median diameter of 3 to 100 μm into a cylindrical shape. By making the median diameter of the inorganic powder 3 μm or more, it is possible to suppress the generation of residues of the vapor deposition material, so that the vapor deposition rate can be sufficient and the film can be formed for a long time. By controlling the thickness to 100 μm or less, the sintered compact can be made tough and splash can be suppressed. Further, by making the shape cylindrical, splash caused by local high temperatures can be suppressed.
The median diameter of the inorganic powder is more preferably 3 to 10 μm. The median diameter means a diameter in which the large side and the small side are equal when the powder is divided into two from a certain particle diameter. In the present invention, the median diameter is calculated based on the laser diffraction scattering method.

Splash refers to a phenomenon in which vapor deposition material that has not been vaporized is scattered as high-temperature fine particles due to thermal shock caused by heating during vapor deposition or pressure of gas generated from the inside. When such high-temperature fine particles collide with the vapor deposition substrate, pinholes are generated in the vapor-deposited PVD inorganic layer, resulting in a problem that gas barrier properties and transparency are lowered. By doing so, the occurrence of the problem can be prevented.
Therefore, the gas barrier film including the specific PVD layer can be of a higher quality by setting the shape of the vapor deposition material as described above.

  The lower limit of the thickness of the specific PVD inorganic layer is generally 0.1 nm, preferably 0.5 nm, more preferably 1 nm, more preferably 10 nm, and the upper limit is generally 500 nm, preferably 100 nm, more preferably. Is 50 nm. The thickness of the specific PVD inorganic layer is preferably 0.1 nm or more and 500 nm or less, more preferably 10 nm or more and 500 nm or less, further preferably 10 nm or more and 100 nm or less, and particularly preferably 10 nm, from the viewpoint of gas barrier properties and film productivity. It is 50 nm or less. The thickness of the specific PVD inorganic layer can be measured using fluorescent X-rays, and can be specifically performed by the method described later.

  The specific PVD inorganic layer is formed by vacuum deposition among physical vapor deposition. The vacuum evaporation method is preferable in that a uniform thin film having a high gas barrier property can be obtained as compared with the sputtering-based physical evaporation method. Heating means used in the vacuum deposition method include resistance heating by a heater, induction heating, electron beam heating, among these, since electron beam heating is likely to cause cracking or collapse of the deposited material due to local overheating, From this viewpoint, direct heating or induction heating with a heater or the like is preferable. The heating temperature of a vapor deposition material is 900-1600 degreeC normally, Preferably it is 1200-1400 degreeC.

[PVD inorganic layers other than specific PVD inorganic layers]
Both the first form and the second form may have a PVD inorganic layer other than the specific PVD inorganic layer (hereinafter sometimes referred to as “general PVD inorganic layer”).
As an inorganic substance constituting the general PVD inorganic layer, the inorganic substance includes silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, or oxides, carbides, nitrides or mixtures thereof. From the point of gas barrier properties, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxide carbide, diamond-like carbon are preferable. Etc. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable because they can stably maintain high gas barrier properties, and silicon oxide (SiOx) is particularly preferable. The PVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.
Moreover, various conditions, such as the thickness of a general PVD inorganic layer, the shape of vapor deposition material, can be made the same as that of a specific PVD inorganic layer, and the suitable conditions of various conditions can also be made the same.

[Inorganic layer formed by chemical vapor deposition (CVD)]
In the second embodiment of the present invention, a CVD inorganic layer is formed on the PVD inorganic layer. By the CVD inorganic layer, defects of the general PVD inorganic layer and slight defects of the specific PVD layer are considered to improve gas barrier properties and interlayer adhesion.
In the second embodiment of the present invention, the PVD inorganic layer itself, the CVD inorganic layer, and the PVD inorganic layer are laminated in this order, so that the CVD inorganic layer itself hardly contributes directly to the gas barrier property. On the other hand, in order to exert the sealing effect on the lower layer and the anchor effect on the upper layer, compared with the case where the PVD inorganic layer is simply formed thick or the PVD inorganic layers or the CVD inorganic layers are laminated. , Gas barrier properties are dramatically improved.
In addition, in order to make the said effect more effective, it is preferable that a PVD layer is a specific PVD layer.
In the second embodiment of the present invention, the CVD inorganic layer and the PVD inorganic layer are formed after the PVD inorganic layer is formed. The formation of the CVD inorganic layer and the PVD inorganic layer is further repeated once or more. Can be done. That is, in the present invention, from the viewpoint of quality stability, it is preferable that the PVD inorganic layer, the CVD inorganic layer, and the PVD inorganic layer further have one or more structural units composed of the CVD inorganic layer and the PVD inorganic layer. The number of units is more preferably 1 to 3, and further preferably 1 to 2.

  As the chemical vapor deposition method, the plasma CVD method is preferable because it is necessary to increase the film formation rate to achieve high productivity and to avoid thermal damage to the film substrate.

In the present invention, the CVD inorganic layer has a carbon content measured by X-ray photoelectron spectroscopy (XPS method) of 20 at. %, Preferably 10 at. %, More preferably 5 at. %. By setting the carbon content to such a value, the surface energy of the inorganic layer is increased, and the adhesion between the inorganic layers is not hindered. Therefore, the bending resistance and peel resistance of the barrier film are improved.
The carbon content of the CVD inorganic layer is 0.5 at. % Or more, preferably 1 at. % Or more, more preferably 2 at. % Or more is more preferable. Since the intermediate layer contains a small amount of carbon, the stress is efficiently relaxed and the curl of the gas barrier film of the present invention is reduced.
From the above points, the carbon content in the CVD inorganic layer is preferably 0.5 at. % Or more and 20 at. %, More preferably 0.5 at. % Or more and 10 at. %, More preferably 0.5 at. % Or more and 5 at. %, More preferably 1 at. % Or more and 5 at. %, More preferably 2 at. % Or more and 5 at. It is in the range of less than%. Here, “at.%” Indicates an atomic composition percentage (atomic%).

There is no restriction | limiting in particular as a method of achieving the carbon content measured by the said X-ray photoelectron spectroscopy (XPS method) in this invention, For example, the method achieved by selecting the raw material in CVD, a raw material, and reaction gas Examples thereof include a method of adjusting by the flow rate and ratio of (oxygen, nitrogen, etc.), a method of adjusting by the pressure during film formation and input power, and the like.
A specific method for measuring the carbon content by X-ray photoelectron spectroscopy (XPS method) is as described later.

  Examples of the inorganic substance constituting the CVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, and the like, oxides, carbides, nitrides, or mixtures thereof. In view of gas barrier properties and adhesion, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxycarbide, titanium oxide, diamond-like carbon Etc. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable because high gas barrier properties can be stably maintained. The CVD inorganic layer may contain one kind of the inorganic substance or two or more kinds.

  As a raw material for forming a CVD inorganic layer made of silicon oxide or the like, for example, a silicon compound can be cited. Moreover, a titanium compound is mentioned as a raw material for CVD inorganic layer formation which consists of titanium oxide etc. If it is a compound such as a silicon compound or a titanium compound, it can be used in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use with a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent.

  Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and diethyldimethoxy. Silane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (Dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, diethylamino Trimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, tris (Dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1, 3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyl Limethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane , Hexamethyldisiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium inorganic compounds such as titanium oxide and titanium chloride, titanium alkoxides such as titanium tetrabutoxide, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and tetramethyl titanate, Examples include titanium organic compounds such as titanium chelates such as titanium lactate, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethylacetoacetate and titanium triethanolaminate.

In order to ensure the sealing effect on the PVD inorganic layer, the CVD inorganic layer is preferably composed of two or more layers, more preferably 2 to 5 layers.
The thickness of the CVD inorganic layer is less than 20 nm as measured by a cross-sectional TEM method. By being in the above range, the intermolecular force between the PVD inorganic layers acts effectively, thereby improving the adhesion. At the same time, since the production rate by the chemical vapor deposition method can be increased to the same level as that of the vacuum vapor deposition method, the production efficiency can be improved and the production equipment can be downsized and simplified, so that an inexpensive barrier film can be produced. From the above viewpoint, the thickness of the CVD inorganic layer is preferably less than 10 nm, more preferably less than 5 nm, and even more preferably less than 3 nm.

Further, the lower limit value of the thickness of the CVD inorganic layer is preferably 0.01 nm, more preferably 0.1 nm, as a minimum film thickness for exhibiting a sealing effect on the PVD inorganic layer. Preferably, it is 0.5 nm. If the thickness is within the above range, the adhesion and gas barrier properties are good, which is preferable. When the thickness of the CVD inorganic layer is 0.1 nm or more, the effect of sealing the open pores of the lower PVD inorganic layer described above is exhibited at the same time that the surface becomes smooth and the upper PVD inorganic layer is deposited. Since the surface diffusion of the vapor deposition particles becomes good and the particles are deposited more densely, the barrier property is further improved.
From the above viewpoint, the thickness of the CVD inorganic layer is preferably 0.01 nm or more and less than 20 nm, more preferably 0.1 nm or more and less than 20 nm, further preferably 0.1 nm or more and less than 10 nm, It is particularly preferably 0.1 nm or more and less than 5 nm, and particularly preferably 0.1 nm or more and less than 3 nm.

  In the present invention, in the adjacent CVD inorganic layer and PVD inorganic layer, the thickness ratio [CVD inorganic layer thickness / PVD inorganic layer thickness] is preferably 0.0001 to 0.2, It is more preferably 0.0005 to 0.1, and further preferably 0.001 to 0.1. By setting [CVD inorganic layer thickness / PVD inorganic layer thickness] to 0.0001 or more, effects such as a sealing effect and stress relaxation by the CVD inorganic layer can be obtained. In addition, by setting [CVD inorganic layer thickness / PVD inorganic layer thickness] to 0.2 or less, the base material is formed when the PVD inorganic layer and the CVD inorganic layer are continuously formed by the Roll to Roll process. Therefore, it is not necessary to greatly reduce the transfer speed in accordance with the CVD inorganic layer having a low film formation rate, and the productivity can be prevented from being lowered.

The surface roughness (measured by AFM) of the PVD inorganic layer is preferably about 5 nm or less, because vapor deposition particles are densely deposited, which is preferable for the expression of barrier properties. At this time, by setting the thickness of the CVD inorganic layer to be less than the above value, the crest portion of the vapor deposition particles is covered only very thinly while filling open vacancies in the valley portions between the vapor deposition particles (or partially). Therefore, the adhesion between the PVD inorganic layers can be further enhanced.
The thickness of the CVD inorganic layer can be measured by a cross-sectional TEM method using a transmission electron microscope (TEM), and specifically by the method described later.

The CVD inorganic layer is formed by evaporating the raw material compound and introducing it into a vacuum apparatus as a raw material gas, and direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, tripolar structure. Plasma, microwave plasma, downstream plasma, columnar plasma, plasma assisted epitaxy, remote plasma, etc. can be used to generate plasma. Among these, a radio frequency (RF) plasma apparatus is preferable from the viewpoint of plasma stability, and a remote plasma apparatus capable of obtaining a dense inorganic layer with a small surface roughness is preferable.
In addition to the plasma CVD method, a known method such as a thermal CVD method, a Cat-CVD method (catalytic chemical vapor deposition), a photo CVD method, or an MOCVD method can be used. Among these, the thermal CVD method and the Cat-CVD method are preferable because they are excellent in mass productivity and film formation quality.

[Anchor coat layer]
In the gas barrier film of the present invention, an anchor coat layer is preferably provided between the substrate and the PVD inorganic layer in order to improve the adhesion between the substrate and the PVD inorganic layer. As a component of the anchor coat layer, from the viewpoint of productivity, polyester alcohol, urethane resin, acrylic resin, nitrocellulose resin, silicone resin, polyvinyl alcohol resin such as vinyl alcohol resin and ethylene vinyl alcohol resin, etc. Resin, isocyanate group-containing resin, carbodiimide resin, alkoxyl group-containing resin, epoxy resin, oxazoline group-containing resin, styrene resin, polyparaxylylene resin, etc. can be used alone or in combination of two or more. it can.
From the group consisting of polyester resin, urethane resin, acrylic resin, nitrocellulose resin, silicone resin and isocyanate group-containing resin, from the viewpoint of gas barrier properties and adhesion when used as a gas barrier film as the resin. It is preferable to use at least one selected resin. Among these, at least one resin selected from the group consisting of polyester resins, urethane resins, acrylic resins, and isocyanate group-containing resins is more preferable, and polyester resins and acrylic resins are more preferable.
The molecular weight of the polymer constituting the resin is preferably a number average molecular weight of 3,000 to 50,000, more preferably 4,000 to 40,000, even more preferably from the viewpoint of gas barrier properties and adhesion. 5,000 to 30,000.
Moreover, it is preferable to mix | blend and harden | cure a hardening | curing agent to an anchor coat layer. Examples of the curing agent include isocyanate compounds.
Examples of the isocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as xylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene diisocyanate, tolidine diisocyanate, and naphthalene diisocyanate. Etc. From the viewpoint of gas barrier properties and adhesion, a polyisocyanate having two or more isocyanate groups is preferable, and a polyisocyanate having three or more isocyanate groups is more preferable.
In addition, various known additives can be blended in the anchor coat layer. Examples of such additives include aqueous epoxy resins, alkyl titanates, antioxidants, weathering stabilizers, UV absorbers, antistatic agents, pigments, dyes, antibacterial agents, lubricants, inorganic fillers, antiblocking agents, and the like. be able to.

The thickness of the anchor coat layer provided on the substrate is usually 0.1 to 5000 nm, preferably 1 to 2000 nm, more preferably 1 to 1000 nm. If it is within the above range, the slipperiness is good, there is almost no peeling from the base material due to the internal stress of the anchor coat layer itself, and a uniform thickness can be maintained, and also in the adhesion between layers Are better.
Moreover, in order to improve the applicability | paintability and adhesiveness of the anchor coating agent to a base material, you may perform surface treatments, such as normal chemical treatment and electrical discharge treatment, before a base material's application | coating.

[Protective layer]
Moreover, it is preferable that the gas barrier film of this invention forms a protective layer in the uppermost layer in the side in which each said inorganic layer was formed.
Specific examples of the protective layer include polyester resins, urethane resins, acrylic resins, vinyl alcohol resins such as polyvinyl alcohol resins and ethylene vinyl alcohol resins, ethylene-unsaturated carboxylic acid copolymers, Examples of the resin layer include vinyl ester resins, nitrocellulose resins, silicone resins, epoxy resins, styrene resins, isocyanate group-containing resins, carbodiimide group-containing resins, alkoxyl group-containing resins, and oxazoline group-containing resins. Of these, from the viewpoint of improving the gas barrier property of the inorganic layer, a resin layer of a water-soluble resin is preferable, and examples of the water-soluble resin include polyvinyl alcohol resin, ethylene vinyl alcohol resin, and ethylene-unsaturated carboxylic acid copolymer. At least one selected from coalescence is preferred. Resin used for the said protective layer may be used individually by 1 type, and may be used in combination of 2 or more type.
The protective layer contains one or more inorganic particles selected from particulate inorganic fillers and layered inorganic fillers such as silica sol, alumina sol and other inorganic oxide sols in order to improve gas barrier properties, abrasion resistance, and slipperiness. can do.
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 bar coater, or a coating method using a spray can be used. Moreover, after forming an inorganic layer, a structural unit layer, etc. in a base material, you may immerse in a coating liquid and may form a protective layer. After coating, a uniform protective layer is formed by evaporating the solvent using a known drying method such as hot air drying at a temperature of about 80 to 200 ° C., heat roll drying, or infrared drying. The

[Configuration of Gas Barrier Film A (First Form)]
As the gas barrier film of the first aspect of the present invention, the following embodiments can be preferably used from the viewpoint of gas barrier properties and adhesion.
(1) Base material / AC / specific PVD inorganic layer / protective layer (2) Base material / AC / specific PVD inorganic layer / specific PVD inorganic layer / protective layer (3) Base material / specific PVD inorganic layer / protective layer (4 ) Base material / specific PVD inorganic layer / specific PVD inorganic layer (5) base material / specific PVD inorganic layer (6) base material / AC / specific PVD inorganic layer / general PVD inorganic layer / protective layer “AC” refers to the anchor coat layer and “/” refers to the interface of the layers.

[Configuration of Gas Barrier Film B (Second Embodiment)]
As the gas barrier film of the present invention, the following embodiments can be preferably used from the viewpoint of gas barrier properties and adhesion.
(1) Base material / AC / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer (2) Base material / AC / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic Layer (3) Base material / AC / Specific PVD inorganic layer / CVD inorganic layer / Specific PVD inorganic layer / CVD inorganic layer / Specific PVD inorganic layer / CVD inorganic layer / Specific PVD inorganic layer (4) Base material / AC / Specific PVD Inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer (5) substrate / AC / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer (6) Base material / AC / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer

(7) Base material / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer (8) Base material / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer (9) Base material / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer (10) base material / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer (11) substrate / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer (12) substrate / specific PVD inorganic layer / CVD inorganic Layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / CVD inorganic layer / specific PVD inorganic layer / protective layer (13) substrate / AC / specific PVD inorganic layer / CVD inorganic layer / general PVD inorganic layer / protection Layer In the embodiment, “AC” refers to the anchor coat layer, and “/” refers to the interface of the layers.

In this invention, the various gas-barrier laminated | multilayer film which laminated | stacked the additional structural layer further on the said structural layer as needed can be used according to a use.
As a normal embodiment, a gas barrier laminate film in which a plastic film is provided on the inorganic layer or protective layer is used for various applications. The thickness of the plastic film is usually 5 to 500 μm, preferably 10 to 200 μm, depending on the application, from the viewpoints of mechanical strength, flexibility, transparency as a substrate of the laminated structure. . In addition, the width and length of the film are not particularly limited and can be appropriately selected according to the use, but in producing an industrial product using a barrier film, it is possible to produce a long product, From the viewpoint of productivity and cost advantage, such as being able to produce many products in a single process, it is desirable that the width and length of the film be long. The film width is preferably 0.6 m or more, more preferably 0.8 m or more, further preferably 1.0 m or more, and the film length is preferably 1000 m or more, more preferably 3000 m or more, and further preferably 5000 m or more. Further, for example, by using a resin capable of heat sealing on the surface of the inorganic layer or the protective layer, heat sealing becomes possible, and it can be used as various containers. Examples of the resin that can be heat sealed include known resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer, ionomer resin, acrylic resin, and biodegradable resin.

  Another embodiment of the gas barrier laminate film is one in which a print layer is formed on the coated surface of the inorganic layer or the protective layer and a heat seal layer is further laminated thereon. As the printing ink for forming the printing layer, aqueous and solvent-based resin-containing printing inks can be used. Here, examples of the resin used in the printing ink include acrylic resins, urethane resins, polyester resins, vinyl chloride resins, vinyl acetate copolymer resins, and mixtures thereof. Furthermore, for printing inks, antistatic agents, light shielding agents, ultraviolet absorbers, plasticizers, lubricants, fillers, colorants, stabilizers, lubricants, antifoaming agents, crosslinking agents, antiblocking agents, antioxidants, etc. These known additives may be added.

Although it does not specifically limit as a printing method for providing a printing layer, Well-known printing methods, such as an offset printing method, a gravure printing method, and a screen printing method, can be used. For drying the solvent after printing, a known drying method such as hot air drying, hot roll drying, or infrared drying can be used.
It is also possible to laminate at least one paper or plastic film between the printing layer and the heat seal layer. As a plastic film, the thing similar to the thermoplastic polymer film as a base material used for the gas barrier film of this invention can be used. Among these, paper, polyester resin, polyamide resin or biodegradable resin is preferable from the viewpoint of obtaining sufficient rigidity and strength of the laminate.

  The total light transmittance (JIS K7361-1) of the gas barrier film is preferably 85% or more, and more preferably 90% or more.

The L ^* value in the L ^* a ^* b ^* display color system of the gas barrier film is preferably 90 or more, and more preferably 95 or more. The b ^* value is preferably −2 or more, more preferably −1 or more, preferably less than 3, more preferably 2.5 or less, and 2 or less. Further preferred.

<Method for producing gas barrier film A>
In the gas barrier film of the first aspect of the present invention, a vapor deposition material containing silicon and / or silicon monoxide is installed in a crucible made of a material in which the inner surface of the storage portion is inactive against silicon monoxide gas, It can manufacture by forming an inorganic layer in the at least one surface of a base material by the vacuum evaporation method which vaporizes a vapor deposition material by heating.

The PVD inorganic layer is formed under reduced pressure, preferably while transporting the film, in order to form a dense thin film. The pressure when forming the PVD inorganic layer is preferably 1 × 10 ⁻⁷ to ¹ Pa, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ Pa, from the viewpoints of vacuum exhaust capability and barrier properties. It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² Pa. If it is in the said range, sufficient gas-barrier property will be acquired, and it is excellent also in transparency, without generating a crack and peeling in a PVD inorganic layer.
Moreover, it is preferable that the conveyance speed of the base material at the time of forming a PVD inorganic layer from the point of productivity shall be 100 m / min or more.
The above pressure and speed conditions are the same for the specific PVD layer and the general PVD layer.

<Method for producing gas barrier film B>
In the gas barrier film of the second aspect of the present invention, an inorganic layer by vacuum deposition, an inorganic layer by chemical vapor deposition, and an inorganic layer by vacuum deposition are formed in this order on at least one surface of the substrate. , One or more of the inorganic layers formed by the vacuum deposition method, and a deposition material containing silicon and / or silicon monoxide is installed in a crucible made of a material in which the inner surface of the storage portion is inert to the silicon monoxide gas, It can manufacture by forming by the vacuum evaporation method which vaporizes a vapor deposition material by heating.

The formation of the CVD inorganic layer is preferably performed under reduced pressure in order to form a dense thin film, and is preferably 10 Pa or less, more preferably 1 × 10 ^{−2 to} 10 Pa, and still more preferably from the viewpoint of film formation speed and barrier properties. Is 1 × 10 ^{−1 to 1} Pa.
Moreover, it is preferable that the conveyance speed of the base material at the time of forming a CVD inorganic layer is 100 m / min or more from a viewpoint of productivity improvement, and it is more preferable that it is 200 m / min or more. Although there is no upper limit in particular regarding the said conveyance speed, 1000 m / min or less is preferable from a viewpoint of stability of film conveyance.
In addition, in order to improve water resistance and durability, the CVD inorganic layer can be subjected to a crosslinking treatment by electron beam irradiation.

From the viewpoint of gas barrier properties and productivity, it is preferable to continuously form the PVD inorganic layer, the CVD inorganic layer, and the PVD inorganic layer under reduced pressure. Further, from the same viewpoint, it is preferable to perform the formation of the CVD inorganic layer at a transport speed of the substrate of 100 m / min or more, particularly while transporting the film, preferably transporting the film. That is, in the present invention, after the formation of each thin film, the pressure in the vacuum chamber is returned to the vicinity of the atmospheric pressure, and the subsequent process is not performed again by evacuation. Preferably it is done.
In addition, when repeating formation of each said inorganic layer, it is preferable to carry out continuously under reduced pressure. Similarly, when repeatedly laminating the PVD inorganic layer itself in the first embodiment of the present invention, it is preferably carried out continuously under reduced pressure in the same apparatus.

  In the present specification, the expression “X to Y” (X and Y are arbitrary numbers) means “X or more and Y or less” unless otherwise specified.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples.
In addition, the following evaluation was performed about the gas barrier film and gas barrier laminated film obtained by the following Examples and Comparative Examples, and the results are shown in Table 1.
<Water vapor transmission rate>
Using two gas barrier laminated films with a moisture permeable area of 10.0 cm x 10.0 cm square, making a bag with about 20 g of anhydrous calcium chloride as a hygroscopic agent with the vapor deposition layer side facing outside, and sealing all sides Place the bag in a constant humidity device at a temperature of 40 ° C. and a relative humidity of 90% RH, measure the mass from the 14th day when the moisture permeability is stable to the 30th day at intervals of 72 hours or more, and the elapsed time and bag weight after the 14th day The moisture permeability (g / m ² / day) was calculated from the slope of the regression line.

<Total light transmittance>
According to JIS K7361-1, the total light transmittance of the gas barrier film was measured with an integrating sphere turbidimeter “ND-2000” manufactured by Nippon Denshoku Industries Co., Ltd.

<L ^* a ^* b ^* Display color system L ^* value, b ^* value>
The L ^* value and b ^* value of the gas barrier film were measured with a spectral color difference meter “SD-600” manufactured by Nippon Denshoku Industries Co., Ltd.

<Film thickness of inorganic layer formed by vacuum vapor deposition (PVD)>
Measurement of the film thickness of the inorganic layer was performed using fluorescent X-rays. This method uses the phenomenon of emitting fluorescent X-rays peculiar to atoms when they are irradiated with X-rays, and knowing the number (amount) of atoms by measuring the intensity of emitted fluorescent X-rays. Can do. Specifically, a thin film having two known thicknesses is formed on the film, the specific fluorescent X-ray intensity emitted for each is measured, and a calibration curve is created from this information. Similarly, the fluorescent X-ray intensity was measured for the measurement sample, and the film thickness was measured from the calibration curve.

<Film thickness of CVD inorganic layer>
A sample was prepared by an epoxy resin-embedded ultrathin section method, and measured with a cross-sectional TEM apparatus “JEM-1200EXII” manufactured by JEOL Ltd. under an acceleration voltage of 120 KV. As for the thickness of the CVD inorganic layer of 10 nm or less, since it is difficult to obtain an accurate value even in the measurement by the cross-sectional TEM method, a relatively thick CVD inorganic layer of 20 nm or more formed under the same film forming conditions is used. The film forming rate per unit transport speed is calculated by measuring by the cross-sectional TEM method, and the thickness when the film is formed at the transport speed described in the examples is the calculated value.
<Carbon content of CVD inorganic layer>
Using an XPS analyzer K-Alpha manufactured by Thermo Fisher Scientific Co., Ltd., the binding energy is measured by XPS (X-ray photoelectron spectroscopy) and converted from the peak areas corresponding to Si2P, C1S, N1S, O1S, etc. Thus, the elemental composition (at.%) Was calculated. The carbon content of the CVD inorganic layer was evaluated by reading the value of the CVD inorganic layer portion of the XPS chart.

Example 1
(1) Production of Vapor Deposition Material Precipitated SiO was produced with a vacuum aggregator, and the deposited SiO was pulverized with a pulverizer and then classified to obtain SiO powder having a median diameter of 3 μm. Subsequently, it pressure-molded in the metal mold | die, and obtained the column-shaped molded object whose fracture strength at the time of pressurization is 5 MPa or more, diameter 25mm, and height 15mm. Next, the obtained molded body was sintered at about 1000 ° C. under the conditions of an inert atmosphere and atmospheric pressure to obtain a vapor deposition material (powdered SiO sintered body).

(2) Production of gas barrier film and gas barrier laminated film As a base material, a biaxially stretched polyethylene naphthalate film (made by Teijin DuPont, “Q51C12”) having a width of 1.2 m, a length of 12000 m, and a thickness of 12 μm was used. On the corona-treated surface, a mixture containing an isocyanate compound (“Coronate L” manufactured by Nippon Polyurethane Industry) and a saturated polyester (“Byron 300” manufactured by Toyobo Co., Ltd., number average molecular weight 23000) in a 1: 1 mass ratio was applied and dried. An anchor coat layer having a thickness of 100 nm was formed.
Next, the inner surface of a cylindrical graphite crucible (bulk density: 1.8 Mg / m ³ , thermal conductivity: 135 W / (m · K)) is placed in a crucible covered with silicon carbide to a thickness of about 100 μm. Vapor deposition material is installed, SiO is vaporized by heating under a vacuum of 2 × 10 ⁻³ Pa using a vacuum vapor deposition apparatus, and a 35 nm thick SiOx vacuum vapor deposition film (specific PVD inorganic layer) is formed on the anchor coat layer. Formed. The sum of the inner surface areas of all the crucibles in this step was 0.3 m ² .

  Next, without returning the pressure to atmospheric pressure, HMDSN (hexamethyldisilazane), nitrogen gas, and Ar gas were introduced at a molar ratio of 1: 7: 7, and the plasma was inorganicized under a vacuum of 0.4 Pa. A CVD inorganic layer (SiOCN (silicon oxycarbonitride) was formed on the layer surface (thickness 4 nm), and the carbon content of the CVD inorganic layer was 4%.

Next, without returning the pressure to atmospheric pressure, the vapor deposition material was placed in the crucible under a vacuum of 2 × 10 ⁻³ Pa, SiO was vaporized by heating, and SiOx having a thickness of 35 nm was formed on the CVD inorganic layer. A specific PVD inorganic layer was formed to obtain a gas barrier film. The sum of the inner surface areas of all the crucibles in this step was 0.3 m ² .
Further, a urethane-based adhesive ("AD900" manufactured by Toyo Morton Co., Ltd. and "CAT-RT85" in a ratio of 10: 1.5) was applied to the inorganic layer side of the obtained film, dried, and dried. An adhesive resin layer having a thickness of about 3 μm is formed, and an unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film-CTP 1146” manufactured by Toyobo Co., Ltd.) is laminated on the adhesive resin layer to obtain a gas barrier laminate film. It was.

Example 2
In Example 1, a gas barrier film and a gas barrier laminated film were produced in the same manner except that the laminated film was made of base material / anchor coat layer / specific PVD inorganic layer / adhesive resin layer / polypropylene film (Example) The structure which remove | excluded the specific PVD layer on a CVD inorganic layer and a CVD layer from 1 gas-barrier film).

Example 3
In Example 2, a gas barrier film and a crucible made of cylindrical tantalum (bulk density: 16.7 Mg / m ³ , thermal conductivity: 57.5 W / (m · K)) were used in the same manner. A gas barrier laminate film was produced.

Comparative Example 1
A gas barrier film and a gas barrier laminate were similarly prepared in Example 1, except that the crucible was a cylindrical graphite crucible (bulk density: 1.8 Mg / m ³ , thermal conductivity: 135 W / (m · K)). A film was prepared.

Comparative Example 2
In Example 2, the gas barrier film and the gas barrier property were the same except that the crucible was made of a cylindrical graphite crucible (bulk density: 1.8 Mg / m ³ , thermal conductivity: 135 W / (m · K)). A laminated film was produced.

  In the above examples and comparative examples, the conveyance speed of the base material when forming the PVD layer and the CVD inorganic layer was 100 m / min.

  The gas barrier film of the present invention can be used for packaging articles that require blocking of various gases such as water vapor and oxygen, for example, packaging materials for food and pharmaceuticals, materials for solar cells and electronic paper, and packaging materials for electronic devices. Can be suitably used. Moreover, the gas barrier film of the present invention has good productivity and can be industrially produced.

Claims (10)

  At least one surface of the substrate has an inorganic layer formed by a vacuum vapor deposition method, and the inorganic layer formed by the vacuum vapor deposition method is made of a material whose inner surface of the storage portion is inert to silicon monoxide gas. A gas barrier film, which is formed by installing a vapor deposition material containing silicon and / or silicon monoxide in a crucible and vaporizing the vapor deposition material by heating.   An inorganic layer formed by a vacuum deposition method, an inorganic layer formed by a chemical vapor deposition method, and an inorganic layer formed by a vacuum deposition method in this order on at least one surface of the substrate, and formed by the vacuum deposition method. One or more layers are provided with a vapor deposition material containing silicon and / or silicon monoxide in a crucible made of a material in which the inner surface of the storage part is inert to the silicon monoxide gas, and the vapor deposition material is vaporized by heating. A gas barrier film which is formed by   The gas barrier film according to claim 1 or 2, wherein the inert material is a metal or a metal compound.   The gas barrier film according to claim 3, wherein the metal or metal compound has a melting point of 1600 ° C. or higher.   The gas barrier film according to claim 3, wherein the metal compound is silicon carbide or silicon nitride.   The gas barrier film according to any one of claims 1 to 5, wherein the total light transmittance according to JIS K7361-1 is 85% or more. The gas barrier film according to claim 1, wherein the b ^* value in the L ^* a ^* b ^* display color system is −2.0 or more and less than 3.0.   The vapor deposition material is a vapor deposition material formed by sintering and molding an inorganic powder containing silicon powder and / or silicon monoxide powder having a median diameter of 3 to 100 µm into a cylindrical shape. The gas barrier film according to the description.   A vacuum deposition method in which a deposition material containing silicon and / or silicon monoxide is placed in a crucible made of a material inert to the silicon monoxide gas on the inner surface of the storage portion, and the deposition material is vaporized by heating, A method for producing a gas barrier film, comprising forming an inorganic layer on at least one surface of a material.   An inorganic layer formed by vacuum deposition, an inorganic layer formed by chemical vapor deposition, and an inorganic layer formed by vacuum deposition are formed in this order on at least one surface of the base material. A gas barrier formed by a vacuum deposition method in which a deposition material containing silicon and / or silicon monoxide is placed in a crucible whose inner surface is made of a material inert to silicon monoxide gas, and the deposition material is vaporized by heating. For producing a conductive film.