JP2018108643A - Film laminate, production method of the same, and film deposition apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film laminate including an inorganic layer and an organic layer with high adhesion, a production method of the same, and a film deposition apparatus.SOLUTION: A film laminate F includes a metal compound-containing inorganic layer 2 and an organic layer 3 adjacent to the inorganic layer 2 on a base film 1, in which the organic layer 3 contains a metal identical to the metal in the metal compound, and an average content of the metal in the thickness direction of the organic layer 3 is in a range of 0.1-1,000 mass ppm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film laminate, a manufacturing method thereof, and a film forming apparatus. Specifically, the present invention relates to a film laminate including an inorganic layer and an organic layer with high adhesion, a manufacturing method thereof, and a film forming apparatus capable of forming an inorganic layer and an organic layer with high adhesion.

Conventionally, a functional film having a functional layer formed on a base film has been widely used.
A gas barrier film used as a packaging material for foods, pharmaceuticals, electronic devices and the like is also one of functional films. In the gas barrier film, the inorganic layer formed on the base film shields gas such as water and oxygen in the atmosphere to prevent deterioration of the contents.

A gas barrier layer having a laminated structure of an inorganic layer and an organic layer is known to have high gas barrier properties (see, for example, Patent Document 1).
When organic layers and inorganic layers are alternately laminated by vacuum deposition, sufficient gas barrier properties may not be obtained, so an inorganic layer is formed under a high vacuum pressure, and an organic layer is formed under a lower pressure. A forming method has been proposed (for example, see Patent Document 2).
However, since the inorganic layer and the organic layer are formed in the same vacuum chamber, the material of the inorganic layer is irregularly mixed into the organic layer and the transparency varies depending on the position, the transparency of the entire film is reduced, etc. The film quality was low.

In order to prevent mixing of materials of the organic layer and the inorganic layer, the film formation chambers of the organic layer and the inorganic layer can be separated and a vacuum exhaust unit can be provided in each film formation chamber (see, for example, Patent Document 3).
However, the film laminate in which the inorganic layer and the organic layer are adjacent has low adhesion between the inorganic layer and the organic layer. When placed in an environment of high temperature and high humidity, the adhesiveness is further lowered, the inorganic layer and the organic layer are easily peeled off, and the functionality of the inorganic layer and the organic layer is often lost.

JP 2006-289627 A JP 2007-230115 A JP 2009-270145 A

  This invention is made | formed in view of the said problem and the situation, The solution subject is providing the film laminated body provided with the inorganic layer and organic layer with high adhesiveness, its manufacturing method, and a film-forming apparatus.

  In order to solve the above problems, the present inventor, in the process of studying the cause of the above problems, the organic layer contains the same metal as the metal compound that is the material of the inorganic layer, so that the inorganic layer and the organic layer As a result, it was found that the adhesiveness of the toner was improved, and the present invention was achieved.

That is, the subject concerning this invention is solved by the following means.
1. On a base film, a film laminate comprising an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer,
The organic layer contains the same metal as the metal in the metal compound;
An average content of the metal in a thickness direction of the organic layer is in a range of 0.1 to 1000 ppm by mass.

2. The inorganic layer has a thickness in the range of 3 to 30 nm;
The thickness of the said organic layer exists in the range of 500-5000 nm, The film laminated body of 1st term | claim characterized by the above-mentioned.

  3. The value of the ratio of the thickness of the said organic layer with respect to the thickness of the said inorganic layer exists in the range of 50-500, The film laminated body of Claim 1 or 2 characterized by the above-mentioned.

  4). The film laminate according to any one of Items 1 to 3, wherein the inorganic layer is formed by an atomic layer deposition method.

  5. The average content of the said metal in the thickness direction of the said organic layer exists in the range of 1.0-500 mass ppm, The film as described in any one of Claim 1 to 4 characterized by the above-mentioned. Laminated body.

6). Production of a film laminate that transports a base film to a first film formation chamber and a second film formation chamber to form an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer on the base film A method,
In the first film formation chamber, a raw material gas of the metal compound is supplied to form the inorganic layer,
In the second film formation chamber, the source gas of the organic layer is supplied and the source gas of the metal compound is supplied to form the organic layer containing the same metal as the metal in the metal compound,
The supply amount of the source gas of the metal compound in the second film forming chamber is controlled so that the average content of the metal in the thickness direction of the organic layer is in the range of 0.1 to 1000 ppm by mass. The manufacturing method of the film laminated body characterized by the above-mentioned.

7). Forming the inorganic layer having a thickness in the range of 3 to 30 nm in the first film formation chamber;
7. The method for producing a film laminate according to claim 6, wherein the organic layer having a thickness in the range of 500 to 5000 nm is formed in the second film forming chamber.

8). A film forming apparatus that transports a base film to a first film forming chamber and a second film forming chamber to form an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer on the base film. And
In the first film formation chamber, a raw material gas of the metal compound is supplied to form the inorganic layer,
In the second film formation chamber, the source gas of the organic layer is supplied and the source gas of the metal compound is supplied to form the organic layer containing the same metal as the metal in the metal compound,
The supply amount of the source gas of the metal compound in the second film forming chamber is controlled so that the average content of the metal in the thickness direction of the organic layer is in the range of 0.1 to 1000 ppm by mass. A film forming apparatus.

9. Forming the inorganic layer having a thickness in the range of 3 to 30 nm in the first film formation chamber;
9. The film forming apparatus according to claim 8, wherein the organic layer having a thickness in a range of 500 to 5000 nm is formed in the second film forming chamber.

  By the above means of the present invention, it is possible to provide a film laminate comprising an inorganic layer and an organic layer with high adhesion, a method for producing the same, and a film forming apparatus.

  Although the manifestation mechanism or action mechanism of the effect of the present invention is not clear, the same metal as the inorganic layer in the organic layer is set so that the average content in the thickness direction is within the range of 0.1 to 1000 ppm by mass. In addition, it is presumed that the uniform inclusion increases the interaction between the metal in the organic layer and the metal in the inorganic layer, and improves the adhesion between the organic layer and the inorganic layer.

Sectional drawing which shows the structure of the film laminated body of embodiment of this invention The front view which shows the structure of the film-forming apparatus of embodiment of this invention A perspective view showing a configuration example of a non-contact type roller Front view showing a configuration of a first film forming chamber in which an inorganic layer is formed by a plasma CVD method Front view showing the configuration of a film forming apparatus when the second film forming chamber is provided with a source gas supply unit

  The film laminate of the present invention comprises, on a base film, an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer, and the organic layer contains the same metal as the metal in the metal compound. The average content of the metal in the thickness direction of the organic layer is in the range of 0.1 to 1000 ppm by mass. This feature is a technical feature common to the inventions according to claims 1 to 9.

As an embodiment of the present invention, from the viewpoint of obtaining sufficient functionality and durability of the inorganic layer and the organic layer, the thickness of the inorganic layer is in the range of 3 to 30 nm, and the thickness of the organic layer is , Preferably in the range of 500 to 5000 nm.
From the same viewpoint, the value of the ratio of the thickness of the organic layer to the thickness of the inorganic layer is preferably in the range of 50 to 500.

  Moreover, it is preferable that the average content of the said metal in the thickness direction of the said organic layer exists in the range of 1.0-500 mass ppm from a viewpoint of improving the adhesiveness of an inorganic layer and an organic layer more.

  The film laminate of the present invention transports a base film to a first film formation chamber and a second film formation chamber, an inorganic layer containing a metal compound on the base film, and an organic layer adjacent to the inorganic layer, In the first film formation chamber, the raw material gas of the metal compound is supplied to form the inorganic layer, and in the second film formation chamber, Supplying the source gas of the organic layer and supplying the source gas of the metal compound to form the organic layer containing the same metal as the metal in the metal compound, the thickness in the thickness direction of the organic layer Film laminate manufacturing method or film formation for controlling the supply amount of the raw material gas of the metal compound in the second film formation chamber so that the average metal content is in the range of 0.1 to 1000 ppm by mass Depending on the device Can.

Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail.
In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Film laminate]
FIG. 1 shows a structural example of a film laminate F that is an embodiment of the present invention.
As shown in FIG. 1, the film laminate F includes an inorganic layer 2 on the base film 1 and an organic layer 3 on the inorganic layer 2.
As long as the inorganic layer 2 and the organic layer 3 are adjacent to each other, the stacking order is not limited to the stacking order shown in FIG. 1, and the inorganic layer 2 may be stacked on the organic layer 3.
Moreover, although FIG. 1 has shown the example provided with the one inorganic layer 2 and the organic layer 3, respectively, the film laminated body F is provided with the some inorganic layer 2 and the organic layer 3 which were laminated | stacked alternately. Also good.

[Base film]
The base film 1 is a base material for the film laminate F.
As the base film 1, a film-like resin, glass, metal, or the like can be used as long as it has flexibility. Especially, since it is lightweight, resin is preferable and resin with high transparency is preferable. When the transparency of the resin is high and the transparency of the base film 1 is high, a highly transparent film laminate F can be obtained. As a functional film such as a gas barrier film, the film laminate F can be converted into an organic EL ( It can be preferably used for an electronic device such as an electro luminescence element.

Examples of the resin that can be used as the base film 1 include methacrylate ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, and polyether ether. Ketone, polysulfone, polyethersulfone, polyimide (PI), polyetherimide and the like can be mentioned. Of these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferable from the viewpoint of cost and availability.
The base film 1 may be a laminated film in which two or more of the above resins are laminated.

  The resin base film 1 can be manufactured by a conventionally known general manufacturing method. For example, an unstretched resin base material that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, by dissolving the resin used as a material in a solvent, casting (casting) it onto an endless metal resin support, drying, and peeling, an unstretched film that is substantially amorphous and not oriented is used as a base. It can be obtained as film 1.

  The unstretched film can be stretched in the film transport direction (MD: Machine Direction) or the width direction (TD: Transverse Direction) perpendicular to the transport direction, and the resulting stretched film can be used as the base film 1. Examples of the stretching method include known methods such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, and tubular simultaneous biaxial stretching. Although a draw ratio can be suitably selected according to resin used as a raw material, both the conveyance direction and the width direction are preferably in the range of 2 to 10 times.

  The base film 1 may be the above-described unstretched film or a stretched film. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression. Since optical functions such as retardation of the base film 1 can be adjusted by stretching, it is preferable to use a stretched film when adjustment is necessary.

The base film 1 may be subjected to relaxation treatment, off-line heat treatment, and the like from the viewpoint of improving dimensional stability.
The relaxation treatment is preferably carried out in the tenter extending in the width direction after the heat setting in the stretching step, or in the step up to winding after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, and more preferably in the range of 100 to 180 ° C.

  The method of off-line heat treatment is not particularly limited. For example, a roller transport method using a plurality of roller groups, an air transport method in which air is blown and floated on a film (specifically, heated air is supplied from a plurality of slits on one side of the film surface). Or a method of spraying on both surfaces), a method of using radiant heat by an infrared heater, a conveying method of hanging the film under its own weight and winding it down. Good dimensional stability can be obtained by making the conveyance tension during heat treatment as low as possible to promote thermal shrinkage. As the treatment temperature, a temperature range of (Tg + 50) to (Tg + 150) ° C. is preferable. Tg here refers to the glass transition temperature of the base film 1.

  The thickness of the base film 1 is not specifically limited, When obtaining the thin film laminated body F, it can be 200 micrometers or less. From the viewpoint of obtaining a thinner film laminate F, the thickness is preferably 100 μm or less, and more preferably in the range of 20 to 100 μm.

[Inorganic layer]
The inorganic layer 2 contains a metal compound and can be formed, for example, as a gas barrier layer, an insulating layer, a refractive layer having a refractive index difference with respect to the substrate of the electronic device, or the like. In particular, the inorganic layer 2 formed as a gas barrier layer has low adhesion to the organic layer 3, and when peeling occurs, gas such as water and oxygen penetrates through the peeled portion, and the gas barrier performance is remarkably lowered. Therefore, the inorganic layer 2 having high adhesion with the organic layer 3 is advantageous as a gas barrier layer.

When the inorganic layer 2 is a gas barrier layer, the gas barrier layer has a water vapor permeability measured by a method according to JIS-K-7129-1992 (25 ± 0.5 ° C., relative humidity 90 ± 2% RH). ) Preferably exhibits a gas barrier property of 0.010 (g / m ² · 24 h) or less, and more preferably 0.001 (g / m ² · 24 h) or less. Moreover, it is preferable that the oxygen permeability measured by the method based on JIS-K-7126-1987 is 1 * 10 < ^-3 > (ml / m < ² > * day * atm) or less. The water vapor permeability can also be measured by the MOCON method, the calcium corrosion method described in JP-A-2005-283561, and the like.

As a material for the inorganic layer 2, metal compounds such as metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, metal carbonitrides and the like can be used alone or in combination of two or more.
Examples of the metal in the metal compound that can be used for the inorganic layer 2 include aluminum (Al), titanium (Ti), silicon (Si), zirconium (Zr), hafnium (Hf), lanthanum (La), niobium (Nb), Examples include tantalum (Ta), magnesium (Mg), zinc (Zn), nickel (Ni), vanadium (V), copper (Cu), cobalt (Co), iron (Fe), and yttrium (Y).

The thickness of the inorganic layer 2 is preferably in the range of 3 to 30 nm.
If the thickness is 3 nm or more, sufficient functionality of the inorganic layer 2, such as gas barrier properties, can be obtained. Moreover, if thickness is 30 nm or less, durability in high temperature, high humidity will also improve, and sufficient functionality can be maintained over a long period of time.

  A method for forming the inorganic layer 2 is not particularly limited, and an evaporation method, a sputtering method, a plasma CVD method, an atomic layer deposition (ALD) method, or the like can be used. Especially, since the dense inorganic layer 2 with high functionality is obtained, the inorganic layer 2 is preferably formed by the ALD method.

[Organic layer]
The organic layer 3 can be provided on the inorganic layer 2 as a protective layer for preventing damage to the inorganic layer 2. Moreover, the organic layer 3 can also be provided between the base film 1 and the inorganic layer 2 as a base layer for improving the adhesion between the base film 1 and the inorganic layer 2.

The organic layer 3 contains the same metal as the metal in the metal compound contained in the inorganic layer 2, and the average content of the metal in the thickness direction of the organic layer 3 is within a range of 0.1 to 1000 ppm by mass. is there.
If the average content of the metal is 0.1 mass ppm or more, the interaction between the metal in the organic layer 3 and the metal in the inorganic layer 2 is increased, and high adhesion between the organic layer 3 and the inorganic layer 2 is obtained. Moreover, if it is 1000 mass ppm or less, durability of the organic layer 3 under high temperature and high humidity can be improved.
From the viewpoint of further improving the adhesion, the average metal content in the thickness direction of the organic layer 3 is preferably in the range of 1.0 to 500 ppm by mass.

  The measurement method of the average metal content in the thickness direction of the organic layer 3 includes secondary ion mass spectrometry (SIMS), time-of-flight (TOF) SIMS, Auger electron spectroscopy. Methods (AES: Auger Electron Spectroscopy), X-ray Photoelectron Spectroscopy (XPS), Rutherford Backscattering Spectrometry (RBS), Glow Discharge Mass Spectrometry (GDMS), etc. Can be used.

Among these, so-called XPS depth profile measurement is preferable, in which surface composition analysis is sequentially performed while exposing the inside of the sample by using XPS together with rare gas ion sputtering such as argon.
In XPS depth profile measurement, etching is performed at a constant interval from the surface of the organic layer 3 to the interface with the inorganic layer 2 in the thickness direction of the organic layer 3 by rare gas ion sputtering, and surface composition analysis is performed by XPS each time the etching is performed. Thus, a metal distribution curve can be obtained. The vertical axis of the distribution curve is the atomic ratio (at%) of the metal, and the horizontal axis is the etching time (sputtering time). In this metal distribution curve, the etching time is converted into the thickness distance L from the surface of the organic layer 3 in the thickness direction of the organic layer 3 by the etching rate, and the atomic ratio (at%) of the metal is contained ( In terms of (mass), the metal content at each thickness distance L is obtained. The metal content at each thickness distance L from the surface of the organic layer 3 to the interface with the inorganic layer 2 is integrated, and the average value of the obtained integrated values is calculated for the metal in the thickness direction of the organic layer 3. It can obtain | require as average content (mass ppm).

Specific measurement conditions for XPS depth profile measurement include the following measurement conditions.
(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

The thickness of the organic layer 3 is preferably in the range of 500 to 5000 nm.
If the thickness is 500 nm or more, sufficient functionality of the organic layer 3 can be obtained. For example, when the organic layer 3 is formed as a protective layer for the inorganic layer 2, the inorganic layer 2 can be sufficiently protected, and the durability of the inorganic layer 2 under high temperature and high humidity can be improved. Moreover, if thickness is 5000 nm or less, the functionality of the inorganic layer 2 can fully be exhibited, and the organic layer 3 with high transparency can be obtained.

When the thickness of the inorganic layer 2 is expressed as d1 (nm) and the thickness of the organic layer is expressed as d2 (nm), the ratio of the thickness d2 of the organic layer 3 to the thickness d1 of the inorganic layer 2 (d2 / d1) Is preferably in the range of 50 to 500.
If the value of the thickness ratio is within this range, the transparency of the film laminate F can be increased. Moreover, sufficient interaction between the metal in the inorganic layer 2 and the metal in the organic layer 3 is obtained, and sufficient adhesion between the inorganic layer 2 and the organic layer 3 can be obtained.

Although it does not specifically limit as a material of the organic layer 3, Preferably the material which can be used for the film-forming under a vacuum pressure is preferable. By forming a film under vacuum pressure, foreign matter such as dust and dirt in the atmosphere can be prevented between the inorganic layer 2 and the organic layer 3 or into the organic layer 3, and film defects caused by the foreign matter can be reduced. it can. Since the organic layer 3 can be laminated on the clean and highly active inorganic layer 2 immediately after film formation, it is advantageous for improving the adhesion between the inorganic layer 2 and the organic layer 3.
As a preferable material of such an organic layer 3, for example, polyparaxylylene can be used.
When polyparaxylylene is used, polyparaxylylene is heated and evaporated under vacuum pressure, and this vapor is heated to 650 to 700 ° C. and thermally decomposed to generate thermal radicals. Thereby, radical polymerization reaction proceeds and a polyparaxylylene film can be formed.

As a material for the organic layer 3, a polyaddition polymer can also be used.
Examples of the polyaddition polymer include polyurethane having diisocyanate and glycol as monomers, polyurea having diisocyanate and diamine as monomers, and polyamide having diolefin and diamide as monomers.
When using a polyaddition polymer, the two types of monomers are alternately and repeatedly subjected to addition polymerization by evaporating the two types of monomers in a vacuum, thereby forming a polyaddition polymer film.

  A curable polymer can also be used as the material of the organic layer 3. Among them, an acrylic polymer that has high transparency, has a high curing rate, and is cured at room temperature can be preferably used. Examples of the acrylic polymer include polymethyl methacrylate oligomers. Moreover, ring-opening polymerization type photocationically curable polymers such as epoxy-based and oxetane-based polymers are also preferable because they have low internal stress due to volume shrinkage during curing and excellent adhesion.

[Method for producing film laminate and film forming apparatus]
FIG. 2 shows a configuration example of the film forming apparatus 100 according to the embodiment of the present invention.
As shown in FIG. 2, the film forming apparatus 100 includes a pressure adjustment chamber 10, a pretreatment chamber 20, a first film formation chamber 30, a second film formation chamber 40, and a pressure adjustment chamber 50.
The film forming apparatus 100 unwinds the roll body of the base film 1 by the unwinder 61 and sequentially conveys the base film 1 to the pressure adjusting chamber 10, the pretreatment chamber 20, and the first film forming chamber 30. The inorganic layer 2 is formed in the film chamber 30. Further, the film forming apparatus 100 transports the base film 1 to the second film forming chamber 40, forms the organic layer 3 in the second film forming chamber 40, and manufactures the film laminate F. Thereafter, the film forming apparatus 100 transports the base film 1 to the pressure adjusting chamber 50 and the winder 62 and winds the base film 1 by the winder 62 to form a roll body of the film laminate F.

As shown in FIG. 2, the film forming apparatus 100 includes two unwinders 61 and two winders 62 so that a plurality of rolls of the base film 1 can be continuously conveyed.
Specifically, when the unwinding of the first roll of the base film 1 is finished by one unwinder 61, the one unwinder 61 is replaced by the other unwinder 61 by the rotational movement. Then, the second roll base film 1 is unwound by the other unwinder 61 so as to connect the rear end of the first roll base film 1 and the front end of the second roll base film 1. Similarly, when the winder 62 finishes winding the first roll of the base film 1 with one winder 62, the winder 62 immediately replaces the other winder 62 and winds the second roll of base film 1.

The film forming apparatus 100 transports the base film 1 with a roller until it is wound by the winder 62 after being unwound by the unwinder 61. In order to suppress film defects of the inorganic layer 2 and the organic layer 3, this roller is preferably a non-contact type roller that can transport the base film 1 without contacting the inorganic layer 2 or the like.
FIG. 3 shows an example of a non-contact type roller.
As shown in FIG. 3, the non-contact type roller has a smaller diameter at the center in the axial direction than at the end. When the base film 1 is transported, the non-contact type roller can be transported without damaging the inorganic layer 2 and the like formed at the center in the width direction because the non-contact type roller contacts only both ends of the base film 1 in the width direction.

The pressure adjustment chambers 10 and 50 adjust the pressure environment of the base film 1. Specifically, the pressure adjustment chamber 10 is adjusted from the atmospheric pressure to the vacuum pressure, and the pressure adjustment chamber 50 is adjusted from the vacuum pressure to the atmospheric pressure.
The pressure adjusting means of the pressure adjusting chamber 10 is not particularly limited, and may be a plurality of connected decompression units as described in Japanese Patent Application Laid-Open No. 2010-17430, or described in International Publication No. 2008/102868. It may be a buffer chamber. The buffer chamber is a chamber in which the transport path of the base film 1 is partitioned by a partition provided with an orifice-shaped seal roll, and the pressure in each chamber partitioned by the partition can be adjusted independently. For example, in the case of the pressure adjustment chamber 10, the pressure environment of the base film 1 that has passed through each chamber is gradually reduced from the atmospheric pressure to the reduced pressure by gradually reducing the pressure in each chamber toward the downstream in the transport direction. The pressure can be reduced.

As shown in FIG. 2, the pretreatment chamber 20 is provided with a vacuum pump 21 and an inert gas supply unit 22, and the exhaust gas from the vacuum pump 21 and the inert gas supplied from the supply unit 22 The pressure environment is adjusted under a certain reduced pressure.
By conveying the base film 1 to the pretreatment chamber 20, the pressure environment of the base film 1 adjusted under reduced pressure in the pressure adjustment chamber 10 can be stabilized.

[First deposition chamber]
Although the configuration of the first film formation chamber 30 varies depending on the method of forming the inorganic layer 2, FIG. 2 shows the configuration of the first film formation chamber 30 when the inorganic layer 2 is formed by the ALD method. In the ALD method, two or more kinds of raw materials are alternately supplied onto the base film 1 and a film forming process for reacting the respective raw materials is repeated for a plurality of cycles, and an atomic layer (may be a molecular layer of a compound) is used for each cycle. Is formed by depositing layers one by one.
As shown in FIG. 2, the first film formation chamber 30 includes three chambers 31 to 33 that are partitioned by a partition wall. The partition is provided with an opening so that the base film 1 can be conveyed.

The chambers 31 and 32 are respectively provided with source gas supply pipes 311 and 321 for the inorganic layer 2. The chambers 31 and 32 are provided with vacuum pumps 312 and 322, respectively, and the inside of the chambers 31 and 32 is adjusted to a vacuum pressure.
The degree of vacuum in the first film forming chamber 30 can usually be adjusted within a range of 0.1 to 1000 Pa.
The chamber 33 is provided with an inert gas supply pipe 331 and an exhaust pipe 332. A rare gas or the like can be used as the inert gas, but a nitrogen gas or the like can also be used if the reactivity with the raw material gas supplied into the chambers 31 and 32 is low.

At the time of film formation, the base film 1 is conveyed to the chamber 31 and a raw material gas of a metal compound that is a material of the inorganic layer 2 is supplied to adsorb the raw material molecules on the surface of the base film 1. Thereafter, the base film 1 is transported to the chamber 32, a raw material gas for reforming treatment is supplied, and the raw material molecules adsorbed on the surface of the base film 1 are reformed. By this one cycle of film formation treatment, a metal compound film of one atomic (molecular) layer can be formed.
Further, the base film 1 is transported to the chamber 31 and a plurality of cycles of film formation are performed until the inorganic layer 2 having a target thickness is obtained.
Excess source gas that could not be adsorbed on the base film 1 in each chamber 31 or 32 can be removed (purged) by the inert gas supplied into the chamber 33 while passing through the chamber 33.

  The source gas of the metal compound supplied to the chamber 31 is aluminum (Al), titanium (Ti), silicon (Si), zirconium (Zr), hafnium (Hf), lanthanum (La), niobium (Nb), tantalum ( Source gas of metal compound such as Ta), magnesium (Mg), zinc (Zn), nickel (Ni), vanadium (V), copper (Cu), cobalt (Co), iron (Fe), yttrium (Y) Can be used.

For example, when a film of a metal compound such as aluminum oxide (Al ₂ O ₃ ) or aluminum nitride is formed by a reforming process, the source gas supplied to the chamber 31 includes aluminum and can be vaporized. Can be used without restrictions. Examples of such an aluminum compound include aluminum chloride (Al ₂ Cl ₆ ), trimethylaluminum (Al (CH ₃ ) ₃ , abbreviation TMA), triethylaluminum (abbreviation TEA), trichloroaluminum, and the like.

In the case where a film of a metal compound such as silicon oxide (SiO ₂ ) or silicon nitride (SiN) is formed by the modification treatment, the source gas supplied to the chamber 31 is trisilane (Si ₃ H ₈ ), disilane (Si ₂ ). H ₆ ), monosilane (SiH ₄ ), monochlorosilane (SiH ₃ Cl), dichlorosilane (SiH ₂ Cl ₂ ), hexachlorodisilane (Si ₂ Cl ₆ ), tetrachlorosilane (SiCl ₄ ), trichlorosilane (SiHCl ₃₎ ), Etc., tetrakisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₄ ), trisdimethylaminosilane (Si [N (CH ₃ ) ₂ ] ₃ H), bisdiethylaminosilane (Si [N (C ₂ H) _{5) 2] 2 H 2)} , Bicester tertiary butyl amino silane _(SiH 2 [N _{(C 4 H 9)] 2} ) aminosilane _{such, Si (OC 2 H 5)} 4, SiH 2 Cl 2, Si (NO 3) ₄ or the like can be used.

When forming a film of a metal compound such as titanium oxide (TiO ₂ ), titanium nitride, or titanium carbonitride by the modification treatment, source gases supplied to the chamber 31 include TiF ₄ , titanium tetrachloride (TiCl ₄ ), TiBr _4, TiI _4, tetrakis dimethylamino titanium _{([(CH 3) 2 N} ] 4 Ti), tetrakis (diethylamino) titanium _{Ti [N (C 2 H 5} ) 2] 4, Ti [N (C 2 H 5 CH 3) ] _4, titanium (IV) isopropoxide _{(Ti [(OCH) (CH} 3) 2] 4) and the like can be used.

Further, as the raw material gas for the reforming process supplied to the chamber 32, when the reforming process is oxidation, water (H ₂ O), oxygen, ozone (O ₃ ), methanol, ethanol, or the like is used. it can. When the reforming process is nitriding, nitrogen, ammonia (NH ₃ ), or the like can be used. These gases may be used in combination with hydrogen (H ₂₎ gas.

In the case of forming the inorganic layer 2 as a gas barrier layer, from the viewpoint of enhancing gas barrier properties, aluminum oxide, titanium oxide, silicon oxide, zirconium oxide, zinc oxide, magnesium oxide (MgO), hafnium oxide (HfO ₂ ), It is preferable to form a metal oxide film such as lanthanum oxide (La ₂ O ₃ ). Aluminum oxide and titanium oxide using trimethylaluminum, titanium tetrachloride, or the like as a source gas are particularly preferable because the molecular weight is suitable for repairing the unevenness of the film and the coverage is improved.

In addition, a source gas of a metal compound is supplied to each of the chambers 31 and 32, a chamber for reforming treatment is provided between the chamber 31 and the chamber 32, plasma is generated in each chamber for reforming, The material molecules adsorbed in the chambers 31 and 32 may be modified. This film forming method is called PE (Plasma Enhanced) ALD method.
The inorganic layer 2 may be formed not only by the PEALD method but also by the thermal ALD method.

The formation method of the inorganic layer 2 is not limited to the ALD method, and a plasma CVD method or the like can also be used.
FIG. 4 shows a configuration example of the first film formation chamber 30B when the plasma CVD method is used.
As shown in FIG. 4, a pair of rollers 351 are arranged in the first film formation chamber 30 </ b> B so as to face each other, and a gas supply unit 352 for the raw material gas of the inorganic layer 2 is provided adjacent to each roller 351. ing.

  The pair of rollers 351 are each connected to a power source 353 and incorporate a magnetic field generator 354. By supplying the source gas from the gas supply unit 352 and applying a voltage between the rollers 351 by the power source 353, plasma is generated in the discharge space between the rollers 351, and the plasma reaction of the source gas proceeds to each roller. The inorganic layer 2 is formed on the base film 1 conveyed by 351. Since a magnetic field is formed around each roller 351 by the magnetic field generator 354, plasma is generated along the magnetic field lines of this magnetic field. Electrons are confined in the film formation space by the electric and magnetic fields in the discharge space, and high-density plasma is generated, so that the film formation efficiency is improved.

  In the first film formation chamber 30, the inorganic layer having a thickness in the range of 3 to 30 nm from the viewpoint of obtaining sufficient functionality of the inorganic layer 2 and improving durability under high temperature and high humidity as described above. 2 is preferably formed.

  When the inorganic layer 2 is formed by the plasma CVD method, the same source gas as that used in the ALD method can be used as the source gas to be supplied. In the case of forming a silicon compound film, hexamethyldisiloxane or the like can be used. It is also possible to use a silicon-containing polymer gas.

[Second deposition chamber]
The configuration of the second film forming chamber 40 differs depending on the method of forming the organic layer 3, but FIG. 2 shows the configuration when the vapor deposition method is used.
As shown in FIG. 2, a vapor deposition source 41 is provided in the second film formation chamber 40. Further, the inside of the second film forming chamber 40 is adjusted to a vacuum pressure by a vacuum pump 42 provided in the second film forming chamber 40.
The degree of vacuum of the second film forming chamber 40 can be usually in the range of 0.01 to 100 Pa.
In the second film forming chamber 40, the raw material gas for the organic layer 3 is supplied onto the base film 1 by the vapor deposition source 41, and the raw material for the organic layer 3 is vapor-deposited to form the organic layer 3.

  In the second film forming chamber 40, as described above, the organic layer 3 having a thickness in the range of 500 to 5000 nm may be formed from the viewpoint of obtaining sufficient functionality of the organic layer 3 and high transparency. preferable.

[Material gas supply means]
In the second film forming chamber 40, the film forming apparatus 100 supplies a raw material gas for the organic layer 3 and a raw material gas for the metal compound contained in the inorganic layer 2. In order to supply the source gas of the metal compound contained in the inorganic layer 2 to the second film forming chamber 40, the partition wall between the first film forming chamber 30 and the second film forming chamber 40 has a structure as shown in FIG. An opening 71 can be provided. FIG. 2 shows an example in which an opening 71 is provided in the partition wall on the side of the chamber 31 for supplying the source gas of the metal compound among the chambers 31 and 32 of the first film formation chamber 30. When supplying the source gas of the metal compound also to the chamber 32, the opening 71 may be provided also in the partition wall on the chamber 32 side.

By adjusting the pressure _{(P 30> P 40)} than the pressure _{P 40} in the pressure _{P 30} in the first film forming chamber 30 in the second film forming chamber 40, through the opening 71, the first film forming The source gas of the metal compound supplied to the chamber 30 flows into the second film forming chamber 40 and is taken into the organic layer 3. In addition, this pressure adjustment can also prevent the source gas of the organic layer 3 from flowing from the second film formation chamber 40 to the first film formation chamber 30.

  The means for supplying the source gas of the metal compound to the second film forming chamber 40 is not limited to this, and a source gas supply unit 72 is provided in the second film forming chamber 40 as in the film forming apparatus 200 shown in FIG. The source gas of the metal compound contained in the inorganic layer 2 can be supplied by the source gas supply unit 72. 5 has the same configuration as the film forming apparatus 100 shown in FIG. 2 except that a source gas supply unit 72 is provided instead of the opening 71. The same components are denoted by the same reference numerals.

[Material gas control means]
In the film forming apparatus 100, the metal compound raw material gas in the second film forming chamber 40 is adjusted so that the average metal content in the thickness direction of the organic layer 3 is in the range of 0.1 to 1000 ppm by mass. Control the supply amount.

As shown in FIG. 2, when the source gas is supplied from the first film formation chamber 30 to the second film formation chamber 40 by providing the opening 71, the supply amount of the source gas is the size (area) of the opening 71. , pressure ratio of the pressure _{P 30} in the first film forming chamber 30 to the pressure _{P 40} in the second film forming chamber _{40 (P 30 / P 40)} , the conveying speed of the base film 1, a first film forming chamber 30 first 2 It can be controlled by the temperature difference of the film forming chamber 40 or the like. By keeping the size and pressure ratio of the opening 71 constant, the supply amount of the raw material gas of the metal compound can be made constant, and the metal can be uniformly contained in the organic layer 3.
Further, as a means for controlling the supply amount of the source gas, a blowing means for blowing air from the first film forming chamber 30 to the second film forming chamber 40 at a constant air speed may be installed.

The pressure ratio of the pressure _{P 30} in the first film forming chamber 30 to the pressure _{P 40} in the second film forming chamber _{40 (P 30 / P 40)} , typically, be in the range of 1 to 100, Preferably it exists in the range of 1-10. If it is in this range, a metal can be contained in the organic layer 3 so that the average content of the metal in the thickness direction of the organic layer 3 is in the range of 0.1 to 1000 ppm by mass. In the case the pressure ratio _{(P 30 /} P ₄₀₎ is 1, and the like are used in combination the blowing means, it is preferable to control the supply amount.

The area of the opening 71 can be in the range of 0.01 to 5.00% with respect to the total area of the walls separating the first film formation chamber 30 and the second film formation chamber 40. Within this range, the gas composition composition atmosphere in each film forming chamber can be stabilized without causing a deviation in the gas composition distribution supplied into the second film forming chamber 40.
Specific conditions such as the pressure ratio (P ₃₀ / P ₄₀ ), the size of the opening 71, the transport speed of the base film 1, the temperature difference between the first film forming chamber 30 and the second film forming chamber 40 are experimental. The conditions when the average content of the metal in the thickness direction of the organic layer 3 falls within the range of 0.1 to 1000 ppm by mass may be adopted.

  As shown in FIG. 5, when the source gas of the metal compound is supplied from the source gas supply unit 72 to the second film formation chamber 40, the average metal content in the thickness direction of the organic layer 3 is 0.1 to What is necessary is just to control the supply amount of the raw material gas from the raw material gas supply part 72 uniformly so that it may become in the range of 1000 mass ppm.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

[Film Laminate 1]
As a base film, a polyester film MELINEX ST504 (manufactured by DuPont Teijin Films US Limited) having a width of 50 cm, a thickness of 125 μm, and a length of 500 m was prepared.
The base film was degassed for 3 hours by heating to 80 ° C. under a reduced pressure of 1.33 Pa (0.01 Torr).
On the base film after the deaeration treatment, an inorganic layer and an organic layer were formed as follows using the film forming apparatus 100 shown in FIG.

First, a base film was set on the unwinder 61 of the film forming apparatus 100 shown in FIG. 2, and the tip of the base film was conveyed to the winder 62 and wound up and fixed. Thereafter, the base film was sequentially transferred to the pressure adjustment chamber 10 and the pretreatment chamber 20.
A plurality of decompression units described in JP 2010-174370 A was used for the pressure adjustment chambers 10 and 50 of the film forming apparatus 100. In the pressure adjusting chamber 10, each pressure reducing unit was depressurized, and the pressure was adjusted so that the pressure was reduced to an atmospheric pressure at the inlet of the pressure reducing unit, a pressure reducing environment of 50 Pa at the outlet, and gradually reduced from the inlet to the outlet. In the pressure adjusting chamber 50, the pressure was adjusted so that the pressure reduction unit had a reduced pressure environment of 50 Pa, the outlet was under atmospheric pressure, and the pressure gradually increased from the inlet to the outlet.

Next, the base film was transferred to the first film formation chamber 30, and an inorganic layer was formed in the first film formation chamber 30.
Specifically, the base film is supplied by supplying trimethylaluminum gas to the chamber 31 of the first film forming chamber 30, supplying water vapor to the chamber 32, and alternately transporting the base film to the chamber 31 and the chamber 32. An aluminum oxide film having a thickness of 8 nm was formed on 1 as an inorganic layer. The chamber 33 was supplied with dry nitrogen gas. The chambers 31 to 33 were adjusted by vacuum pumps 312 and 322 so that the pressure environment was 50 Pa.

Detailed film forming conditions in the first film forming chamber 30 are as follows.
(Deposition conditions)
Source gas of aluminum oxide: Trimethylaluminum Residence time in chamber 31: 4.0 sec / cycle Source gas for reforming treatment: Water Residence time in chamber 32: 4.0 sec / cycle Used in chamber 33 Inert gas: Nitrogen gas Residence time in chamber 33: 5.0 seconds / cycle Aluminum oxide deposition rate: 0.1 nm / cycle Base film transport speed: 5.0 m / min Base film temperature: 80 ° C.
The opening provided in the chamber 31 was set such that the ratio of the area of the opening to the total area of the wall separating the first film forming chamber 30 and the second film forming chamber 40 was 0.1%.

The base film on which the inorganic layer was formed was further transferred to the second film formation chamber 40, and a polymethyl methacrylate film having a thickness of 1000 nm was formed as an organic layer on the base film in the second film formation chamber 40.
Specifically, the second film formation chamber 40 is depressurized to 50.0 Pa by the vacuum pump 42, the heating boat of the vapor deposition source 41 is energized, and the polymethyl methacrylate oligomer set in the heating boat is heated to 40 ° C. Vapor deposited on the base film. After the vapor deposition, a curing process of irradiating with ultraviolet rays was performed to form the polymethyl methacrylate film.

Next, the base film on which the organic layer was formed was conveyed to the pressure adjustment chamber 50, the pressure environment of the base film was returned to atmospheric pressure, and the roll body of the film laminate 1 was obtained by winding it with the winder 62.
When the average content of aluminum in the thickness direction of the organic layer of the film laminate 1 was measured, it was 0.05 mass ppm.

The average aluminum content was determined by XPS depth profile measurement.
In XPS depth profile measurement, by ion sputtering using argon, etching is performed from the surface of the organic layer to the interface with the inorganic layer in the thickness direction of the organic layer, and the surface composition analysis is performed by XPS each time the etching is performed. An aluminum distribution curve was obtained. The distribution curve was prepared with the vertical axis representing the aluminum atomic ratio (at%) and the horizontal axis representing the etching time (sputtering time). In the aluminum distribution curve, the etching time was converted into the thickness distance L from the surface of the organic layer 3 in the thickness direction of the organic layer 3 by the etching rate, and the atomic ratio of aluminum was converted into the content. The aluminum content at the thickness distance L obtained by conversion was integrated, and the average value was obtained as the average aluminum content in the thickness direction of the organic layer.

The measurement conditions for XPS depth profile measurement are as follows.
(Measurement condition)
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

[Film Laminates 2-7]
In the production of the film laminate 1, the pressure in the second film formation chamber 40 is changed stepwise to a low pressure in the range of less than 50.0 Pa and 0.1 Pa or more, and the aluminum in the thickness direction of the organic layer is changed. Except having adjusted average content as shown in following Table 1, it carried out similarly to the film laminated body 1, and manufactured each film laminated body 2-7.

[Film Laminates 8-13]
In manufacture of the said film laminated body 1, the pressure in the 2nd film-forming chamber 40 was 1.0 Pa, the average content of aluminum in the thickness direction of an organic layer was adjusted to 200 mass ppm, and thickness d1 of an inorganic layer The film laminates 8 to 13 were produced in the same manner as the film laminate 1 except that was changed as shown in Table 1 below.
The thickness d1 of the inorganic layer was changed by adjusting the number of cycles of the film forming process in the first film forming chamber 30.

[Film Laminates 14-18]
In manufacture of the said film laminated body 1, the pressure in the 2nd film-forming chamber 40 was 1.0 Pa, the average content of aluminum in the thickness direction of an organic layer was adjusted to 200 mass ppm, and thickness d1 of an inorganic layer And each film laminated body 14-18 was manufactured like the film laminated body 1 except having changed the thickness d2 of the organic layer as shown in Table 1 below.
The thickness d1 of the inorganic layer was changed by adjusting the number of film formation cycles in the first film formation chamber 30.
The thickness d2 of the organic layer was changed by increasing or decreasing the temperature of the polymethyl methacrylate oligomer heating boat in the second film formation chamber 40 within a range of 10 to 100 ° C.

[Film Laminate 19]
In the production of the film laminate 12, the first film formation chamber 30 of the film formation apparatus 100 shown in FIG. 2 is replaced with the first film formation chamber 30B shown in FIG. A film laminate 19 was produced in the same manner as the film laminate 12 except that the silicon film was formed as an inorganic layer.

Detailed film forming conditions by the plasma CVD method are as follows.
(Deposition conditions)
Metal compound raw material gas: Hexamethyldisiloxane (HMDSO)
Supply amount of metal compound material gas: 50 sccm (standard cubic centimeter per minute) (0 ° C, 1 atm standard)
Source gas for reforming treatment: Oxygen gas Supply amount of source gas for reforming treatment: 500 sccm (0 ° C., 1 atm standard)
Vacuum degree in the chamber: 2.0 Pa
Applied power from the power source for plasma generation: 0.9 kW
Power supply frequency for plasma generation: 70 kHz

[Film Laminate 20]
In the production of the film laminate 3, the film forming apparatus 100 shown in FIG. 2 is replaced by the film forming apparatus 200 shown in FIG. A film laminate 20 was produced in the same manner as the film laminate 3 except that.

[Evaluation]
The gas barrier properties of each of the produced film laminates 1 to 20, the adhesion between the inorganic layer and the organic layer, and transparency were evaluated as follows.

[Gas barrier properties]
Each of the film laminates 1 to 20 was stored in a high-temperature and high-humidity tank having a temperature of 50 ° C. and a relative humidity of 80% RH for one week, and then left for 1 day in an environment of a temperature of 25 ° C. and a relative humidity of 40% RH. Thereafter, the water vapor transmission rate (g / m ² · day) at a temperature of 38 ° C. and a relative humidity of 90% RH was measured by the MOCON method using a MOCON water vapor transmission rate measuring device Aquatran (manufactured by MOCON). The measured water vapor transmission rate was ranked as the gas barrier property of each of the film laminates 1 to 20 as follows. The smaller the value of water vapor transmission rate, the higher the gas barrier property, and rank 3 or higher is a practical gas barrier property.
5: Water vapor transmission rate is 0.001 or less 4: Water vapor transmission rate is greater than 0.001 and 0.005 or less 3: Water vapor transmission rate is greater than 0.005 and 0.010 or less 2: Water vapor transmission rate is Greater than 0.010 and less than or equal to 0.100 1: water vapor transmission rate is greater than 0.100

[Adhesion]
The adhesion between the inorganic layer and the organic layer of each film laminate 1 to 20 was measured before and after the high temperature and high humidity treatment. The measurement was performed according to JIS K 5600 5-6 (2004 edition).
Specifically, 10 × 10 square grid-like cuts were made on the organic layer side, which is the outermost surface of each of the film laminates 1 to 20, using a cutter knife and a 1 mm-spacing cutter guide. One square has a size of 1 mm square, and the depth of the cut is a depth reaching the base film through the inorganic layer from the organic layer side.

An 18 mm wide adhesive tape CT405AP-18 (manufactured by Nichiban Co., Ltd.) was affixed onto the cut organic layer, and the adhesive tape was adhered to the gas barrier layer by rubbing the adhesive tape with an eraser. Thereafter, the pressure-sensitive adhesive tape was peeled off in a direction perpendicular to the gas barrier layer, and among 10 × 10 squares, the number of squares from which the gas barrier layer was peeled off from the base film was counted. The rank evaluation of the adhesion between the base film and the gas barrier layer was performed based on the counted number of masses as follows. The smaller the number of peeled masses, the higher the adhesion, and the adhesion of rank 3 or higher is practical.
5: Number of peeled cells is 5 or less 4: Number of peeled cells is 6 or more and 10 or less 3: Number of peeled cells is 11 or more and 15 or less 2: Number of peeled cells is 16 or more and 20 or less 1: Peeled The number of cells is 21 or more

  Then, each film laminated body 1-20 was preserve | saved for one week in the high temperature, high humidity tank of temperature 50 degreeC and relative humidity 80% RH. The adhesion between the inorganic layer and the organic layer of each film laminate 1 to 20 after storage was evaluated in the same manner as before storage.

〔transparency〕
The light transmittance of the wavelength light of 450 nm of each film laminated body 1-20 was measured using the spectrophotometer U-3900 / 3900H. Specifically, the light transmittance was measured at any 10 points of each film laminate 1 to 20, and the absorption of the base film before forming the inorganic layer and the organic layer was canceled from the measured light transmittance. . The average value of each light transmittance after cancellation was calculated | required as the light transmittance of each film laminated body 1-20.

Based on the obtained light transmittance, the transparency of each of the film laminates 1 to 20 was evaluated as follows. When the rank is 3 or more, it can be preferably used for an electronic device.
5: Light transmittance is 92% or more 4: Light transmittance is 90% or more and less than 92% 3: Light transmittance is 87% or more and less than 90% 2: Light transmittance is 83% or more and less than 87% 1: Light transmittance Less than 83%

Table 1 below shows the evaluation results.

  As shown in Table 1 above, by including a metal having an average content in the thickness direction in the range of 0.1 to 1000 ppm by mass in the organic layer, the adhesion is improved, and under high temperature and high humidity. Even if it is placed, it can maintain high adhesion and eventually high gas barrier properties.

F film laminate 1 base film 2 inorganic layer 3 organic layer 100, 200 film forming apparatus 10, 50 pressure adjusting chamber 30 first film forming chamber (ALD method)
30B First film formation chamber (CVD method)
40 Second film forming chamber 61 Unwinder 62 Winder 71 Opening 72 Source gas supply unit

Claims (9)

On a base film, a film laminate comprising an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer,
The organic layer contains the same metal as the metal in the metal compound;
An average content of the metal in a thickness direction of the organic layer is in a range of 0.1 to 1000 ppm by mass. The inorganic layer has a thickness in the range of 3 to 30 nm;
The thickness of the said organic layer exists in the range of 500-5000 nm, The film laminated body of Claim 1 characterized by the above-mentioned.   3. The film laminate according to claim 1, wherein the value of the ratio of the thickness of the organic layer to the thickness of the inorganic layer is in the range of 50 to 500. 4.   The said inorganic layer is formed by the atomic layer deposition method, The film laminated body as described in any one of Claim 1- Claim 3 characterized by the above-mentioned.   The average content of the said metal in the thickness direction of the said organic layer exists in the range of 1.0-500 mass ppm, The film as described in any one of Claim 1- Claim 4 characterized by the above-mentioned. Laminated body. Production of a film laminate that transports a base film to a first film formation chamber and a second film formation chamber to form an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer on the base film A method,
In the first film formation chamber, a raw material gas of the metal compound is supplied to form the inorganic layer,
In the second film formation chamber, the source gas of the organic layer is supplied and the source gas of the metal compound is supplied to form the organic layer containing the same metal as the metal in the metal compound,
The supply amount of the source gas of the metal compound in the second film forming chamber is controlled so that the average content of the metal in the thickness direction of the organic layer is in the range of 0.1 to 1000 ppm by mass. The manufacturing method of the film laminated body characterized by the above-mentioned. Forming the inorganic layer having a thickness in the range of 3 to 30 nm in the first film formation chamber;
The method for producing a film laminate according to claim 6, wherein the organic layer having a thickness in the range of 500 to 5000 nm is formed in the second film formation chamber. A film forming apparatus that transports a base film to a first film forming chamber and a second film forming chamber to form an inorganic layer containing a metal compound and an organic layer adjacent to the inorganic layer on the base film. And
In the first film formation chamber, a raw material gas of the metal compound is supplied to form the inorganic layer,
In the second film formation chamber, the source gas of the organic layer is supplied and the source gas of the metal compound is supplied to form the organic layer containing the same metal as the metal in the metal compound,
The supply amount of the source gas of the metal compound in the second film forming chamber is controlled so that the average content of the metal in the thickness direction of the organic layer is in the range of 0.1 to 1000 ppm by mass. A film forming apparatus. Forming the inorganic layer having a thickness in the range of 3 to 30 nm in the first film formation chamber;
The film forming apparatus according to claim 8, wherein the organic layer having a thickness in a range of 500 to 5000 nm is formed in the second film forming chamber.

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