WO2013168715A1

WO2013168715A1 - Gas barrier film and method for producing gas barrier film

Info

Publication number: WO2013168715A1
Application number: PCT/JP2013/062857
Authority: WO
Inventors: 健太郎杉田
Original assignee: 三菱樹脂株式会社
Priority date: 2012-05-09
Filing date: 2013-05-07
Publication date: 2013-11-14
Also published as: JP2013252700A; TW201402339A; JP6171542B2

Abstract

Provided is a laminated gas barrier film which has outstanding optical characteristics while having adequate gas barrier properties, and has excellent producibility. The gas barrier film comprises on at least one surface of a base material an inorganic layer which is formed by means of vacuum deposition, the inorganic layer which is formed by means of vacuum deposition being formed by using heat to vaporize a vaporization material that is formed by sintering and moulding an inorganic powder having a median diameter of 3-100 µm into a cylindrical shape whereof the diameter is 10-45% of the inner diameter at the bottom part of a crucible and the height is no greater than 45% of the internal height of the crucible.

Description

Gas barrier film and method for producing gas barrier film

The present invention relates to a gas barrier film mainly used as packaging materials for foods and pharmaceuticals, packaging materials for electronic devices, electronic paper, materials for solar cells, and the like, and a method for producing the same.

The gas barrier film generally has a configuration in which a gas barrier layer is formed on one or both sides of a plastic film as a base material. For example, the gas barrier film includes a plastic film formed with a SiOx vapor deposition film.
Vapor deposition material that can form a SiOx vapor deposition film that exhibits high gas barrier properties is obtained by heating a mixture of Si and SiO ₂ and depositing sublimated SiO gas on a deposition substrate, or crushing or polishing the obtained deposited SiO After that, what is molded (precipitation type SiO) is used. Further, there is a case where the precipitated SiO is powdered and sintered (powder sintered mold type SiO) is used.

Precipitation type SiO has a high density and has a very dense structure. For this reason, when this evaporation material is evaporated to form a SiOx evaporation film, the evaporation material which is not vaporized due to the thermal shock caused by heating during evaporation or the pressure of gas generated from the inside is high temperature. There is a problem that a phenomenon (splash phenomenon) in which fine particles are scattered is likely to occur. When such high-temperature fine particles collide with the SiOx vapor-deposited film, pinholes are generated in the SiOx vapor-deposited film, and the gas barrier property and transparency of the gas barrier film having the SiOx vapor-deposited film are reduced. When the gas barrier film is wound around the roll after being formed, the fine particles are wound between the gas barrier films as foreign matters and finally mixed into the product. Moreover, the problem that a through-hole is produced in a gas barrier film base material also arises.

Powder-sintered molding type SiO has an advantage that it is easy to control density and shape from its manufacturing method, and is widely used. However, the powder sintered mold type SiO has a lower density than the precipitation type SiO and becomes brittle in strength, so that a part of it collapses during evaporation in a high temperature atmosphere, and high temperature fine particles are scattered ( (Splash phenomenon) may occur.

JP 2008-133157 A

The problems associated with the splash phenomenon as described above can be fatal when the gas barrier film is used not only for gas barrier performance but also for applications requiring high definition such as display panels and optical applications.

In the production of a gas barrier film by heating vapor deposition, it is most effective to limit the amount of heating in order to form a film while using a deposition type SiO while suppressing the splash phenomenon. However, when the amount of heating is limited, the generation of foreign matters due to the splash phenomenon is reduced, and a gas barrier film having transparency and appearance suitable for optical applications can be obtained. There was a problem that the decrease of the.
Patent Document 1 attempts to reduce the splash phenomenon depending on the particle diameter, the mixing ratio, and the sintering conditions in the production of powder sintered type SiO. However, in Patent Document 1, the heating means is an electron beam, and the level of thermal shock received by the vapor deposition material is much higher than, for example, conventional heating means such as resistance heating. For this reason, in Patent Document 1, the local thermal gradient of the vapor deposition material is increased, the vapor deposition material is liable to crack or collapse, and a splash phenomenon may occur when the vapor deposition material collapses. In addition, Patent Document 1 does not describe the relationship between the splash phenomenon and the performance of the gas barrier film.
The problem to be solved by the present invention is to provide a gas barrier film having a sufficient gas barrier property, excellent optical properties and excellent productivity, and a method for producing the film.

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) Heating a vapor deposition material obtained by sintering and molding an inorganic powder having a median diameter of 3 to 100 μm into a cylindrical shape having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the inner height of the crucible. It is related with the gas-barrier film which is formed by vaporizing.

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. (PVD) has an inorganic layer formed in this order, and at least one of the inorganic layers formed by the vacuum deposition method (PVD) is an inorganic powder having a median diameter of 3 to 100 μm and a diameter of the bottom inner diameter of the crucible. The present invention relates to a gas barrier film, which is formed by vaporizing by heating a vapor deposition material formed by sintering into a cylindrical shape having a height of 10 to 45% and a height of 45% or less of the internal height of the crucible. .

In the present invention, an inorganic powder having a median diameter of 3 to 100 μm is applied to at least one surface of the substrate, the diameter is 10 to 45% of the bottom inner diameter of the crucible, and the height is 45% or less of the inner height of the crucible. The present invention relates to a method for producing a gas barrier film, in which an inorganic layer is formed by a vacuum vapor deposition method in which a vapor deposition material formed by sintering in a cylindrical shape is vaporized by heating.

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. A vacuum deposition method in which at least one vapor deposition material is sintered and molded into a cylindrical shape having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the internal height of the crucible. The present invention relates to a method for producing a gas barrier film.

The present invention provides a gas barrier film having high gas barrier properties, excellent optical characteristics, and excellent productivity, and a method for producing the film.

Crucible cross-sectional schematic diagram.

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. The inorganic layer formed by the vacuum deposition method (PVD) (hereinafter sometimes referred to as “PVD inorganic layer”) is an inorganic powder having a median diameter of 3 to 100 μm and a diameter of 10 to 45 that is the bottom inner diameter of the crucible. %, A vapor deposition material formed by sintering and molding into a cylindrical shape whose height is 45% or less of the internal height of the crucible, and is formed by vaporizing by heating (hereinafter referred to as “specific PVD inorganic layer”) There is a thing).

<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 of the inorganic layers formed by the vacuum deposition method is an inorganic powder having a median diameter of 3 to 100 μm. Is vapor-deposited by heating to form a vapor-deposited material that is sintered and molded into a cylindrical shape having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the internal height of the crucible. It is an inorganic layer (specific PVD inorganic layer).

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

[Base material]
The substrate of the gas barrier film of the present invention is preferably a plastic film. 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 polyolefins; 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, polyesters, polyamides, polyolefins, and biodegradable resins are preferable from the viewpoint of film strength, cost, and the like, and particularly, polyethylene terephthalate (PET) and polyethylene from the viewpoint of surface smoothness, film strength, heat resistance, and the like. Polyesters such as -2,6-naphthalate (PEN) are 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. Moreover, a single layer or a multilayer may be sufficient. 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 viewpoints of mechanical strength, flexibility, transparency and the like 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 is formed by a vacuum deposition method. More specifically, an inorganic powder having a median diameter of 3 to 100 μm is formed with a diameter of 10 to 45% of the inner diameter of the crucible and a height of the inner height of the crucible. A vapor deposition material formed by sintering and molding into a columnar shape of 45% or less is formed on a substrate by vaporizing by heating. Since the splash phenomenon is suppressed in such a specific PVD inorganic layer, a PVD inorganic layer having excellent gas barrier properties and transparency and having the above performance can be obtained while maintaining a high vapor deposition rate. The reason is considered as (1) and (2) below.

(1) First, regarding the median diameter of the inorganic powder constituting the vapor deposition material, if the median diameter of the powder is large, the strength of the sintered molded body does not come out, so the handling is bad and the splash phenomenon due to heat collapse occurs. Likely to happen. Even when the median diameter of the powder is large, the sintering temperature can be raised to increase the density and strength. For example, when the inorganic powder is SiO, Si produced by decomposition of the SiO in the sintering process, It causes the occurrence of a splash phenomenon and reduces the strength of the molded body.
On the other hand, when the particle size of the inorganic powder is small, the strength of the sintered molded body can be exhibited at a lower temperature than when the particle size is large, and the surface area of the molded body is increased, and the transpiration rate from the viewpoint of heating efficiency. Can be high. However, on the other hand, when the particle diameter is small, the generation of vapor deposition residue due to heat evaporation increases. Vapor deposition residue is debris remaining in the crucible after vapor deposition, and when the residue is generated, the vapor deposition rate is reduced.
For example, in the case where the inorganic powder is SiO, the vapor deposition residue is a reaction product with silicon dioxide (SiO ₂ ) or a material constituting the crucible. That is, in the SiO powder sintered vapor deposition material, the oxidized amount (SiO ₂ ) on the grain surface of the SiO powder as a raw material becomes a residue, so that the amount of residue inevitably increases, and at the same time, the oxide film on the grain surface Since this hinders vapor deposition, the vapor deposition rate decreases.
In the present invention, since the inorganic powder having a median diameter of 3 to 100 μm is used as the inorganic powder constituting the vapor deposition material, there is no occurrence of a splash phenomenon due to the excellent strength of the sintered compact, and the generation of a residue. Since the deposition rate can be suppressed, the deposition rate can be made sufficient and the film can be formed for a long time.

(2) Next, regarding the shape of the vapor deposition material (molded body), when the vapor deposition material has corners (vertices), the corners are likely to be hotter than the peripheral portion, so that a splash phenomenon is likely to occur. In this invention, since the shape of vapor deposition material is made into the column shape, the splash phenomenon caused by local high temperature can be suppressed.

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 laminated on the PVD layer on which high-temperature fine particles have collided due to the splash phenomenon, the surface shape of the PVD layer is affected, and a defective portion is also generated in the layer laminated there. In this case, the problem does not occur, and the gas barrier property and transparency of the multilayer laminated product can be improved.

As the inorganic powder constituting the vapor deposition material, one having a median diameter of 3 to 100 μm is used. When the median diameter of the inorganic powder is less than 3 μm, the deposition rate cannot be made sufficient due to the generation of residues, and long-time film formation becomes difficult. On the other hand, when the median diameter exceeds 100 μm, the strength of the sintered molded body is lowered and it becomes difficult to suppress the splash phenomenon.
The median diameter of the inorganic powder is 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.

In terms of the relationship between the vapor deposition material and the crucible, the percentage of [the diameter of the vapor deposition material] / [the inner diameter of the bottom of the crucible] is preferably 10 to 45%, more preferably 15 to 30%. The percentage of [height] / [inner height of crucible] is preferably 45% or less, more preferably 15 to 30%. Also, in the case of a crucible with a crucible opening inner diameter different from the bottom inner diameter of the crucible, the opening inner diameter is the same as or larger than the bottom inner diameter from the viewpoint of deposition residue deposition and deposition rate on the opening. Is preferred.
As shown in FIG. 1, the bottom inner diameter a of the crucible is the diameter of the bottom excluding the thick portion of the crucible material, and refers to the diameter when the bottom is circular, and the bottom is polygonal, elliptical, etc. When the shape is other than a circle, the length of the longest straight line among the straight lines connecting arbitrary points on the outer periphery of the bottom is indicated. The crucible internal height b indicates the distance from the bottom to the opening excluding the thick portion of the crucible material.

The vapor deposition material sintered and molded into a cylindrical shape can be obtained by pressure-molding inorganic powder into a cylindrical shape and then sintering, or by simultaneously performing molding and sintering into a cylindrical shape with a hot press or the like. Although the sintering temperature varies depending on the inorganic material, for example, in the case of silicon monoxide powder, it is about 700 to 1000 ° C. During sintering, a binder may be used to improve moldability. The atmosphere and pressure at the time of pressurization and sintering may be an inert atmosphere and atmospheric pressure, and particularly fine control is unnecessary.

Examples of the inorganic powder include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, carbon, and the like, or oxides, carbides, nitrides, or mixtures thereof. From the viewpoint of gas barrier properties, it is preferably oxidized. Silicon, aluminum oxide, and carbon (for example, a substance mainly composed of carbon such as diamond-like carbon). In particular, silicon monoxide or a mixture of silicon and silicon dioxide or silicon oxide is preferable in that a specific PVD inorganic layer having high gas barrier properties and excellent optical characteristics can be formed at a sufficient deposition rate. Although the said inorganic substance may be used individually by 1 type, you may use it in combination of 2 or more type.
The specific PVD layer formed from such inorganic powder 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 specific PVD inorganic layer is formed by a vacuum deposition method. 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. Examples of the heating means used in the vacuum deposition method include direct heating with a heater, induction heating, and electron beam heating. Among these heating means, since electron beam heating is liable to cause cracking or collapse of the deposited material due to local overheating, direct heating or induction heating with a heater or the like is preferable.
The heating temperature of the vapor deposition material is usually 900 to 1600 ° C., preferably 1200 to 1400 ° C. In the present invention, even if heated to a high temperature, the splash phenomenon does not occur, so that high-speed production is possible.

When heating the vapor deposition material, the vapor deposition material is preferably placed in the crucible. The crucible may be made of graphite, but is preferably made of a material that is inert to the gas generated when the inner surface of the storage portion vaporizes the vapor deposition material. In addition, when the inorganic powder includes silicon powder and / or silicon monoxide powder, it is preferable to use a crucible made of a material in which the inner surface of the storage portion is inactive with respect to silicon monoxide gas. By using a material that is inert to the gas generated when the inner surface of the storage portion vaporizes the vapor deposition material as the crucible, the gas barrier property and the optical characteristics are excellent, and the production stability can be improved. The reason is considered as follows.
For example, 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, performance such as optical performance of the gas barrier film is 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)
Therefore, by using the crucible made of a material that is inert to the gas generated when the inner surface of the storage portion vaporizes the vapor deposition material, there is no impurity or crystal defect in the PVD inorganic layer. A gas barrier film having further excellent gas barrier properties and transparency can be obtained.

The basic configuration of the crucible includes a storage portion 11 in which a vapor deposition material is installed, and an opening 12 through which the vaporized vapor deposition material is discharged to the vapor deposition target (FIG. 1). In the present invention, it is preferable to use a crucible made of a material that is inert to the gas generated when the inner surface 111 of the container vaporizes the vapor deposition material, and the entire surface of the container (the inner surface 111 and the outer surface 112). It is more preferable to use a crucible made of a material that is inert to the gas generated when the vapor deposition material is vaporized.
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 an inert material, and the storage portion made of an inert material is fitted inside the storage portion that becomes the base material. And the whole crucible 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. , High melting point metals such as osmium, iridium, ruthenium, rhodium, metal compounds (carbides, nitrides, oxides) of these refractory metals, carbides such as silicon carbide and boron carbide, silicon nitride, boron nitride, aluminum nitride, etc. One or more selected from nitrides 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 pressure-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 a gas generated from a vapor deposition material. For example, when the gas generated from the vapor deposition material is 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 lower limit of the thickness of the specific PVD inorganic layer is generally 0.1 nm, preferably 0.5 nm, more preferably 1 nm, still 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 in the examples.

[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”).
Examples of the inorganic substance constituting the general PVD inorganic layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, diamond-like carbon, or oxides, carbides, and nitrides alone or a mixture thereof. Among these, from the viewpoint of gas barrier properties, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxynitride, aluminum oxycarbide, diamond-like carbon, etc. are preferable. is there. Among these, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbonitride, and aluminum oxide are more preferable in that high gas barrier properties can be stably maintained, 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, and a pressure, 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.

An example of a raw material for forming a CVD inorganic layer made of silicon oxide or the like is a silicon compound. 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. The solvent may be diluted with a solvent, and an organic solvent such as methanol, ethanol, n-hexane, or a mixed solvent thereof may be used as the solvent.

Examples of the silicon compound include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-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, diethyla Notrimethylsilane, 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, propargy Trimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetra Examples include siloxane, hexamethyldisiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

Examples of titanium compounds 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.

The CVD inorganic layer is preferably composed of two or more layers, more preferably 2 to 5 layers, in order to ensure the sealing effect on the PVD inorganic layer.
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, the production rate by the chemical vapor deposition method can be increased to the same level as that of the vacuum vapor deposition method, so that the production efficiency can be improved and the production equipment can be miniaturized and simplified, and 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. Further, 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 an atomic force microscope (AFM)) of the PVD inorganic layer is preferably about 5 nm or less, because vapor deposition particles are densely deposited, which is preferable for exhibiting 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), specifically by the method described in the examples.

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, known methods such as a thermal CVD method, a Cat-CVD method (catalytic chemical vapor deposition), a photo CVD method, and an MOCVD method can be used. Of 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. may 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, and 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 a normal chemical treatment and electrical discharge treatment, to a base material before application | coating of an anchor coating agent.

[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 resins, ethylene vinyl alcohol resins, 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 heat drying such as hot air drying and hot roll drying at a temperature of about 80 to 200 ° C., or using a known drying method such as 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 selected in the range of 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. . As the plastic film on the protective layer, the same film as exemplified for the substrate can be used.
There is no restriction | limiting in particular in the width | variety and length of a gas-barrier laminated | multilayer film, According to a use, it can select suitably. In addition, when manufacturing industrial products using a barrier film, it is possible to manufacture long products, from the viewpoint of productivity and cost advantages such as being able to manufacture many products in a single process. The width and length of the film are preferably longer. 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.
Moreover, the gas barrier laminate film can be heat sealed by using a resin capable of heat sealing on the surface of the inorganic layer or the protective layer, and can be used as various containers. Examples of heat-sealable resins include known resins such as polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymers, ionomer resins, acrylic resins, and biodegradable resins.

Further, as another embodiment of the gas barrier laminate film, there may be mentioned one in which a printing layer is formed on the coated surface of the inorganic layer or the protective layer, and further a heat seal layer is 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 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 ^* 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 preferably 2 or less. Further preferred.
Incidentally, the L ^* value, a ^* value and b ^* values, L ^* a ^* b ^* color system of L ^* value of JIS Z8729, means that the a ^* and b ^* values, these values JIS It can be measured based on Z8722.

<Method for producing gas barrier film A>
The gas barrier film according to the first aspect of the present invention comprises an inorganic powder having a median diameter of 3 to 100 μm on at least one surface of a substrate, having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of the crucible. It can be manufactured by forming an inorganic layer by a vacuum vapor deposition method in which a vapor deposition material formed by sintering and molding into a cylindrical shape having an inner height of 45% or less is vaporized 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 at the time of 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. The pressure conditions are the same for the specific PVD layer and the general PVD layer.
Moreover, it is preferable that the conveyance speed of the base material at the time of forming a PVD inorganic layer shall be 100 m / min. The specific PVD layer can suppress the splash phenomenon even at a high temperature, and thus can be manufactured at a high speed.

<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, an inorganic powder having a median diameter of 3 to 100 μm, a circle having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the inner height of the crucible. It can be manufactured by forming a vapor deposition material formed by sintering in a columnar shape by a vacuum vapor deposition method that vaporizes 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 further 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 this specification, “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.

<Number of pieces when dropped>
When the vapor deposition material (sintered body) was dropped onto a transparent glass having a height of 30 mm to a thickness of 7 mm, the number of fragments having a size of 150 μm or more scattered from the vapor deposition material was measured.

<Evaporation during heating>
The deposition apparatus of the crystal oscillator method was provided in the vapor deposition apparatus, and the deposition rate was measured. In the table, the percentage when the film forming speed of Example 1 was set to 100% was described, and the evaporation amount during heating was used. In all of the examples and comparative examples, the amount of heating heat was adjusted to be the same, and the amount of evaporation during heating was measured.

<Number of fine particles in the splash>
The number of fine particles per square meter of the gas barrier laminate film was visually inspected, and the number was counted.

<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>
In accordance with 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.

<Film thickness of PVD inorganic layer>
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 area 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. Next, it is pressure-molded in a mold, the breaking strength at the time of pressurization is 5 MPa or more, the diameter is 20% of the inner diameter of the heating cylindrical crucible described later, and the height is the internal height of the heating cylindrical crucible. A 10% cylindrical molded body was obtained. 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 Laminate Film A biaxially stretched polyethylene naphthalate film (made by Teijin DuPont, “Q51C12”) having a thickness of 12 μm was used as a base material, and an isocyanate compound (Japan) An anchor coat layer having a thickness of 100 nm is formed by applying and drying a mixture of polyurethane industry "Coronate L") and saturated polyester (Toyobo "Byron 300", number average molecular weight 23000) in a 1: 1 mass ratio. did.
Next, the above evaporation material is placed in a cylindrical tantalum crucible (bulk density: 16.7 Mg / m ³ , thermal conductivity: 57.5 W / (m · K), bottom inner diameter: 100 mm, internal height: 100 mm). The SiO 2 is evaporated by heating under a vacuum of 2 × 10 ⁻³ Pa using a vacuum deposition apparatus, and a 25.4 nm thick SiOx vacuum deposition film (specific PVD inorganic layer) is formed on the anchor coat layer. And a gas barrier film was obtained. The conveyance speed of the base material was 100 m / min.

Next, a urethane-based adhesive (“AD900” and “CAT-RT85” manufactured by Toyo Morton Co., Ltd. at a ratio of 10: 1.5) was applied to the inorganic layer surface side of the obtained gas barrier film and dried. An adhesive resin layer having a thickness of about 3 μm was formed, and an unstretched polypropylene film having a thickness of 60 μm (“Pyrene Film-CT P1146” manufactured by Toyobo Co., Ltd.) was laminated on the adhesive resin layer, and a gas barrier laminate film Got.

Example 2
In Example 1, a gas barrier film and a gas barrier laminated film were produced in the same manner except that a SiO 2 powder having a median diameter of 10 μm was used and the thickness of the specific PVD inorganic layer was 25.9 nm.

Example 3
In Example 2, the gas barrier film and the gas barrier laminate film were similarly prepared except that the diameter of the cylindrical molded body was 10% of the inner diameter of the above-described heating cylindrical crucible and the thickness of the specific PVD inorganic layer was 25.3 nm. Was made.

Example 4
In Example 1, a gas barrier film and a gas barrier laminated film were prepared in the same manner except that the SiO powder having a median diameter of 100 μm was used and the thickness of the specific PVD inorganic layer was 26.8 nm.

Example 5
In Example 2, the diameter of the cylindrical molded body is 45% of the bottom inner diameter of the heating cylindrical crucible described above, the height is 45% of the internal height of the heating cylindrical crucible, and the thickness of the specific PVD inorganic layer is A gas barrier film and a gas barrier laminated film were produced in the same manner except that the thickness was 26.0 nm.

Example 6
In Example 2, the specific PVD inorganic layer was provided with a thickness of 25.0 nm, and then the molar ratio of HMDSN (hexamethyldisilazane), nitrogen gas, and Ar gas was 1 without returning the pressure to atmospheric pressure. Was introduced at a ratio of 7: 7, and plasma was formed under a vacuum of 0.4 Pa to form a CVD inorganic layer (SiOCN (silicon oxycarbonitride)) on the surface of the inorganic layer (thickness 4 nm). The carbon content of the CVD inorganic layer was 4%. The conveyance speed of the base material in forming the PVD layer and the CVD inorganic layer was 100 m / min.
Next, without returning the pressure to atmospheric pressure, the vapor deposition material is placed in the crucible under a vacuum of 2 × 10 ⁻³ Pa, SiO is evaporated by heating, and SiOx having a thickness of 35 nm is formed on the CVD inorganic layer. The specific PVD inorganic layer was formed to obtain a gas barrier film. Further, using this gas barrier film, a gas barrier laminated film was obtained in the same manner as in Example 1.

Comparative Example 1
In Example 1, a gas barrier film and a gas barrier laminated film were produced in the same manner except that the SiO powder having a median diameter of 1 μm was used and the thickness of the specific PVD inorganic layer was 24.0 nm.

Comparative Example 2
In Example 1, a gas barrier film and a gas barrier laminated film were produced in the same manner except that the SiO powder having a median diameter of 500 μm was used and the thickness of the specific PVD inorganic layer was 28.0 nm.

Comparative Example 3
In Example 2, the height is the same as that of the molded body of Example 2, except that the diameter of the molded body of Example 2 is a square column with one side, and the thickness of the specific PVD inorganic layer is 25.3 nm. In the same manner, a gas barrier film and a gas barrier laminated film were produced.

Comparative Example 4
In Example 1, a SiO powder having a median diameter of 15 μm was used, the diameter of the cylindrical molded body was 7% of the bottom inner diameter of the heating cylindrical crucible, and the thickness of the specific PVD layer was 25.7 μm. Similarly, a gas barrier film and a gas barrier laminated film were produced.

Comparative Example 5
In Example 1, a SiO powder having a median diameter of 15 μm was used, the diameter of the cylindrical molded body was set to 75% of the inner diameter of the bottom of the above-described heating cylindrical crucible, and the thickness of the specific PVD layer was set to 25.9 μm. Similarly, a gas barrier film and a gas barrier laminated film were produced.

Comparative Example 6
In Example 1, SiO powder having a median diameter of 15 μm is used, the diameter of the cylindrical molded body is 10% of the inner diameter of the bottom of the heating cylindrical crucible described above, and the height is 80% of the internal height of the heating cylindrical crucible. %, And a gas barrier film and a gas barrier laminate film were produced in the same manner except that the thickness of the specific PVD layer was 25.3 μm.

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.

Each of Examples 1 to 6 has a low water vapor transmission rate, a high total light transmittance, and a large amount of evaporation during heating. Therefore, it can be confirmed that the gas barrier properties, optical properties, and productivity are excellent.
On the other hand, Comparative Example 1 had a small median diameter of the vapor deposition material, and Comparative Example 4 had a small diameter of the molded material of the vapor deposition material, so that the amount of evaporation during heating was small and the productivity was poor.
Further, in Comparative Examples 2, 3, 5 and 6, all had a splash phenomenon, water vapor transmission rate was high, and total light transmittance was also low. The cause of the splash phenomenon in these comparative examples is that the comparative example 2 has a large median diameter of the vapor deposition material, so that the strength of the molded body is not sufficient. The shape is a quadrangular prism, the apex tends to be locally high, the comparative example 5 has a large diameter of the molded body of the vapor deposition material, and the heat distribution per molded body is large, comparative example 6 In this case, the height of the molded body of the vapor deposition material is high, and the area away from the bottom surface of the crucible increases, and it is considered that heat unevenness occurs in the molded body.

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 laminated film of the present invention has good productivity and can be industrially produced.

DESCRIPTION OF SYMBOLS 1 ... Crucible 11 ... Storage part 12 ... Opening part 111 ... Inside surface 112 of a storage part ... Outer surface of a storage part

Claims

At least one surface of the substrate has an inorganic layer formed by a vacuum vapor deposition method, the inorganic layer formed by the vacuum vapor deposition method is an inorganic powder having a median diameter of 3 to 100 μm, and a diameter of the bottom inner diameter of the crucible. A gas barrier film, which is formed by heating and vaporizing a vapor deposition material formed into a cylindrical shape having a height of 10 to 45% and a height of 45% or less of the inner height of the crucible.
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 formed by sintering and molding an inorganic powder having a median diameter of 3 to 100 μm into a cylindrical shape having a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the inner height of the crucible. A gas barrier film, which is formed by vaporizing a vapor deposition material by heating.
The gas barrier film according to claim 1 or 2, comprising silicon powder and / or silicon monoxide powder as the inorganic powder.
The gas barrier film according to any one of claims 1 to 3, wherein two or more inorganic layers formed by vaporizing the vapor deposition material by heating are laminated.
The gas barrier film according to any one of claims 1 to 4, wherein the total light transmittance according to JIS K7105 is 85% or more.
The gas barrier film according to any one of claims 3 to 5, wherein the vapor deposition material is placed in a crucible made of a material that is inert to the silicon monoxide gas on the inner surface of the storage portion.
The gas barrier film according to claim 6, wherein the inert material is a metal or a metal compound.
The gas barrier film according to claim 7, wherein the melting point of the metal or metal compound is 1600 ° C or higher.
The gas barrier film according to claim 7, wherein the metal compound is silicon carbide or silicon nitride.
On at least one surface of the base material, an inorganic powder having a median diameter of 3 to 100 μm is sintered into a cylindrical shape having a diameter of 10 to 45% of the bottom inner diameter of the crucible and a height of 45% or less of the inner height of the crucible. A method for producing a gas barrier film, wherein an inorganic layer is formed by a vacuum vapor deposition method in which a vapor deposition material formed by molding is vaporized by heating.
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 substrate. Vapor-deposition material obtained by sintering and molding 3 to 100 μm inorganic powder into a cylindrical shape with a diameter of 10 to 45% of the inner diameter of the bottom of the crucible and a height of 45% or less of the inner height of the crucible. A method for producing a gas barrier film, which is formed by a vacuum evaporation method.