JP2014000782A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film which has high denseness with few defects such as fine voids and cracks.SOLUTION: The laminated film including a substrate and a thin-film layer which is formed on at least one surface of the substrate and contains silicon atoms, oxygen atoms, and carbon atoms is characterized in that the thin-film layer is formed by a plasma chemical vapor deposition method using a raw material gas containing an inorganic silane-based gas, a hydrocarbon-based gas, and an oxygen gas. The thin-film layer is preferably formed using a rare gas, an oxygen gas, or their mixture as a discharge gas.

Description

  The present invention relates to a laminated film.

  In order to impart functionality to a film-like substrate, a laminated film in which a thin film layer is formed (laminated) on the surface of the substrate is known. For example, a laminated film provided with a gas barrier property by forming a thin film layer on a plastic film is suitable for filling and packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, there has been proposed a laminated film in which a thin film of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide or the like is formed on one surface of a base film such as a plastic film.

As a method for forming a thin film on the surface of a plastic substrate in this manner, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, vacuum chemical vapor deposition, plasma chemistry, etc. A film forming method such as chemical vapor deposition (CVD) such as vapor deposition is known.
Patent Document 1 discloses a technique for forming a thin film layer on a plastic film by a CVD method using an organic silicon compound gas and an oxygen gas as raw materials.

JP 2008-179102 A

  However, when a thin film layer is formed on a plastic film by the method described in Patent Document 1, a dense thin film layer cannot be formed, and fine voids, cracks, and the like are generated, and gas barrier properties are not sufficient.

  This invention is made | formed in view of the said situation, and makes it a subject to provide a laminated film with high density and few defects, such as a fine space | gap and a crack.

To solve the above problem,
The present invention is a laminated film comprising a substrate and a thin film layer formed on at least one surface of the substrate and containing a silicon atom, an oxygen atom and a carbon atom,
The thin film layer is formed by a plasma chemical vapor deposition method using a raw material gas containing an inorganic silane-based gas, a hydrocarbon-based gas, and an oxygen gas.

  In the laminated film of the present invention, the thin film layer is preferably formed using a rare gas, oxygen gas or a mixture thereof as a discharge gas.

In the laminated film of the present invention, the abundance ratio of silicon atoms (Si), oxygen atoms (O) and carbon atoms (C) in the thin film layer is preferably in the range of the following formulas (1) and (2). .
0.1 <C / Si <0.5 (1)
1.5 <O / Si <1.9 (2)

In the laminated film of the present invention, it is desirable that the thin film layer has an average density of 1.8 g / cm ³ or more.

  In the laminated film of the present invention, it is desirable that a thin film layer is continuously formed on the base material while continuously conveying the long base material.

In the laminated film of the present invention, the distance from the surface of the thin film layer in the film thickness direction of the thin film layer, and the total of silicon atoms, oxygen atoms, and carbon atoms contained in the barrier layer at the point located at the distance Silicon distribution curves showing the relationship between the ratio of the number of silicon atoms to the number of silicon (ratio of number of silicon atoms), the ratio of the number of oxygen atoms (ratio of oxygen atoms), and the ratio of carbon atoms (ratio of carbon atoms), In the oxygen distribution curve and the carbon distribution curve, the following conditions (i) to (iii):
(I) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the following formula (3) in a region of 90% or more in the film thickness direction of the barrier layer. about,
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (3)
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) It is desirable to satisfy all that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  In the laminated film of the present invention, it is desirable that the raw material gas contains a carbon oxide.

  According to the present invention, a laminated film having high density and few defects such as fine voids and cracks is provided.

[Laminated film]
The laminated film of the present invention is a laminated film comprising a substrate and a thin film layer formed on at least one surface of the substrate and containing silicon atoms, oxygen atoms and carbon atoms,
The thin film layer is formed by a plasma chemical vapor deposition method using a source gas containing an inorganic silane-based gas, a hydrocarbon-based gas, and an oxygen gas.

In the laminated film, a thin film layer is formed on one of the two main surfaces of the base material (hereinafter also referred to as “surface on the thin film layer forming side”). The laminated film may have a thin film layer formed not only on one surface of the substrate but also on the other surface (the surface opposite to the one surface).
Moreover, you may have another layer other than the said thin film layer.

The substrate is in the form of a film or a sheet, and examples of the material include a resin or a composite material containing a resin.
Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefins such as polyethylene (PE), polypropylene (PP) and cyclic polyolefin; polyamide; polycarbonate; polystyrene; acrylic resin; Saponified ethylene-vinyl acetate copolymer; polyacrylonitrile; polyacetal; polyimide; polyether sulfide (PES).
Examples of the composite material containing a resin include silicone resins such as polydimethylsiloxane and polysilsesquioxane; glass composite substrates; glass epoxy substrates and the like.
The material of the substrate may be only one kind or two or more kinds.
Among these, the material of the base material is preferably polyester, cyclic polyolefin, polyimide, glass composite substrate, or glass epoxy substrate from the viewpoint of high heat resistance and low coefficient of thermal expansion.

  The base material is preferably colorless and transparent from the viewpoint that light can be transmitted and absorbed. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.

From the viewpoint that the base material can be used as a base material for an electronic device or an energy device, the base material is preferably insulative and preferably has an electrical resistivity of 10 ⁶ Ωcm or more.

  The thickness of the base material can be appropriately set in consideration of the stability when the laminated film is produced. For example, from the viewpoint that the film can be conveyed even in a vacuum, the thickness is preferably 5 to 500 μm. Further, when the thin film layer is formed by the plasma CVD method as will be described later, the thickness of the base material is more preferably 10 to 200 μm because the thin film layer is formed while discharging through the base material. More preferably, it is ˜100 μm.

  Since the said base material improves adhesiveness with a thin film layer, what the surface activation process for cleaning the surface by the side of a thin film layer formation was performed is preferable. Examples of such surface activation treatment include corona treatment, plasma treatment, UV ozone treatment, and flame treatment.

The thin film layer is highly dense and contains silicon atoms, oxygen atoms, and carbon atoms from the viewpoint of reducing defects such as fine voids and cracks. In this case, the thin film layer is preferably composed mainly of a compound represented by the general formula SiO _α C _β . In this general formula, α is selected from positive numbers less than 2, and β is selected from positive numbers less than 2. One or more of α and β in the above general formula may be a constant value or may vary in the thickness direction of the thin film layer.
Further, the thin film layer contains one or more atoms of elements other than silicon atom, oxygen atom and carbon atom, for example, hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. You may do it.

When the thin film layer contains a hydrogen atom in addition to a silicon atom, an oxygen atom, and a carbon atom, the thin film layer preferably contains a compound represented by a general formula of SiO _α C _β H _γ as a main component. In this general formula, α is selected from a positive number less than 2, β is a positive number less than 2, and γ is selected from a positive number less than 6. One or more of α, β, and γ in the above general formula may be a constant value or may vary in the thickness direction of the thin film layer.

The thin film layer is highly dense and reduces defects such as fine voids and cracks when the average atomic ratio in the thin film layer of silicon atoms (Si) and carbon atoms (C) is represented by C / Si. From the viewpoint, it is preferably in the range of 0.1 <C / Si <0.5, more preferably in the range of 0.15 <C / Si <0.45, and 0.2 <C / Si <0. More preferably in the range of 4, more preferably in the range of 0.25 <C / Si <0.35.
In addition, the thin film layer has high density when the average atomic ratio in the thin film layer in silicon atoms (Si) and oxygen atoms (O) is expressed by O / Si, and has few defects such as fine voids and cracks. Therefore, it is preferable to be in the range of 1.5 <O / Si <1.9, more preferably in the range of 1.55 <O / Si <1.85, and 1.6 <O / Si <1. Is more preferably in the range of .8, and particularly preferably in the range of 1.65 <O / Si <1.75.

  The thin film layer is formed by a plasma chemical vapor deposition method (plasma CVD method) as will be described later.

  The thickness of the thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to break when the laminated film is bent. Furthermore, when forming a thin film layer by a plasma CVD method as will be described later, since the thin film layer is formed while discharging through the substrate, it is more preferably 10 to 2000 nm, and preferably 100 to 1000 nm. Further preferred.

The thin film layer included in the laminated film used in the present embodiment preferably has a high average density of 1.8 g / cm ³ or more. In the present specification, the “average density” of the thin film layer is the number of silicon atoms, the number of carbon atoms, the number of oxygen atoms, and the hydrogen forward scattering method (Rutherford Backscattering Spectrometry: RBS) Calculate the weight of the barrier layer in the measurement range from the number of hydrogen atoms determined by Hydrogen Forward Scattering Spectrometry (HFS), and calculate the volume of the barrier layer in the measurement range (product of the ion beam irradiation area and film thickness). It is calculated by dividing.

When the thin film layer has a density of 1.8 g / cm ³ or more, the laminated film has a high density and a structure with few defects such as fine voids and cracks. When the thin film layer is composed of silicon atoms, oxygen atoms, carbon atoms, and hydrogen atoms, the average density of the barrier layer is less than 2.22 g / cm ³ .

  In the present embodiment, a curve indicating the relationship between the distance from the film surface in the film thickness direction and the local atomic ratio of silicon atoms at each distance is referred to as a silicon distribution curve. Similarly, a curve indicating the relationship between the distance from the film surface in the film thickness direction and the local atomic ratio of oxygen atoms at each distance position is referred to as an oxygen distribution curve. A curve indicating the relationship between the distance from the film surface in the film thickness direction and the local atomic ratio of carbon atoms at each distance is referred to as a carbon distribution curve. A curve showing the relationship between the distance from the film surface in the film thickness direction and the sum of the local atomic ratio of oxygen atoms and the total atomic ratio of carbon atoms at each distance is called an oxygen-carbon distribution curve.

The first condition is a condition in which the carbon distribution curve is substantially continuous. The carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the carbon atomic ratio changes discontinuously. Specifically, when the distance from the film surface in the film thickness direction is x [nm] and the atomic ratio of carbon is C [at%], the following formula (1) is preferably satisfied.
| DC / dx | ≦ 1 (1)

  The second condition is a condition in which the carbon distribution curve has at least one extreme value. The extreme value here is the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the film surface in the film thickness direction. The extreme value is the value of the atomic ratio at the point where the atomic ratio of the element changes from increasing to decreasing or when the atomic ratio of the element changes from decreasing to increasing when the distance from the film surface in the film thickness direction is changed. It is. The extreme value can be obtained, for example, based on a measurement result obtained by measuring an atomic ratio at each of a plurality of measurement positions in the film thickness direction. The measurement position of the atomic ratio is set such that the interval in the film thickness direction is, for example, 20 nm or less. The position where the extreme value is taken is a position where the measurement result is changed from increase to decrease, for example, by comparing measurement results at three or more different measurement positions with respect to a discrete data group including the measurement result at each measurement position. It can be obtained by determining the position where the decrease turns to the increase. The position where the extreme value is taken can also be obtained, for example, by differentiating the approximate curve obtained from the above discrete data group. When the interval in which the atomic ratio monotonously increases or decreases monotonically from the position where the extreme value is taken is, for example, 20 nm or more, the atomic ratio at the position moved by 20 nm in the film thickness direction from the position where the extreme value is taken, The absolute value of the difference is, for example, 3 at% or more.

  In the first thin film layer formed so as to satisfy the second condition, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is less than that in the case where the second condition is not satisfied. That is, by satisfying the second condition, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained. When the first thin film layer is formed so that the number of extreme values of the carbon distribution curve becomes two or more, the amount of increase is reduced as compared with the case where the number of extreme values of the carbon distribution curve is one. . Further, when the first thin film layer is formed so that the number of extreme values of the carbon distribution curve is three or more, the increase amount is larger than that in the case where the number of extreme values of the carbon distribution curve is two. Less. When the carbon distribution curve has two or more extreme values, the distance from the film surface in the film thickness direction at the position where the first extreme value is taken, and the second extreme value adjacent to the first extreme value The absolute value of the difference between the position and the distance from the film surface in the film thickness direction is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 1 nm to 100 nm.

  The third condition is a condition in which the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve is 5 at% or more. In the first thin film layer formed so as to satisfy the third condition, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is less than that in the case where the third condition is not satisfied. That is, by satisfying the third condition, an effect of suppressing a decrease in gas barrier property due to bending can be obtained. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 6 at% or more, the above effect is enhanced, and when it is 7 at% or more, the above effect is further enhanced.

  As the absolute value of the difference between the maximum value and the minimum value of the silicon atomic ratio in the silicon distribution curve decreases, the gas barrier property of the first thin film layer tends to improve. From such a viewpoint, the absolute value is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%.

  In the oxygen-carbon distribution curve, when the total of the atomic ratio of local oxygen atoms and the atomic ratio of carbon atoms at each distance position is defined as “total atomic ratio”, the maximum and minimum values of the total atomic ratio As the absolute value of the difference between the two decreases, the gas barrier property of the first thin film layer tends to improve. From such a viewpoint, the total atomic ratio is preferably less than 5 at%, more preferably less than 4 at%, and particularly preferably less than 3 at%.

  When the first thin film layer has a substantially uniform composition in the film surface direction, the gas barrier property of the first thin film layer can be made uniform and improved. The substantially uniform composition means that in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve, the number of extreme values is the same at any two locations on the film surface, and the carbon in each carbon distribution curve. The absolute value of the difference between the maximum value and the minimum value of the atomic ratio is the same or within 5 at%.

The silicon distribution curve, oxygen distribution curve, and carbon distribution curve of the first thin film layer preferably satisfy the following fourth condition. The fourth condition is a condition that alternatively satisfies the fifth condition or the sixth condition in a region of 90% or more of the thickness of the first thin film layer in the silicon distribution curve, oxygen distribution curve, and carbon distribution curve.
The fifth condition is a condition in which the atomic ratio of oxygen is larger than the atomic ratio of silicon and the atomic ratio of silicon is larger than the atomic ratio of carbon. The fourth condition is expressed by the following formula (2).
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (2)
The sixth condition is a condition in which the atomic ratio of carbon is larger than the atomic ratio of silicon and the atomic ratio of silicon is larger than the atomic ratio of oxygen. The fifth condition is expressed by the following formula (3).
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (3)

  The first thin film layer formed to satisfy the fourth condition can exhibit gas barrier properties generally required for an organic EL element. The gas barrier property of the first thin film layer tends to improve as the range in which the fifth condition or the sixth condition is alternatively satisfied in the film thickness of the first thin film layer increases. From such a viewpoint, it is preferable that the range in which the fifth condition or the sixth condition is alternatively satisfied in the film thickness of the first thin film layer is 95% or more of the film thickness of the first thin film layer. More preferably, it is approximately 100% of the thickness of one thin film layer.

  When the above fifth condition is satisfied, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 25 at% or more and 45 at% or less, More preferably, it is 30 at% or more and 40 at% or less. When the above fourth condition is satisfied, the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 33 at% or more and 67 at% or less, More preferably, it is 45 at% or more and 67 at% or less. When the above fourth condition is satisfied, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 3 at% or more and 33 at% or less, More preferably, it is 3 at% or more and 25 at% or less.

  When the above sixth condition is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 25 at% or more and 45 at% or less, More preferably, it is 30 at% or more and 40 at% or less. When the above fifth condition is satisfied, the atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 1 at% or more and 33 at% or less, More preferably, it is 10 at% or more and 27 at% or less. When the above fifth condition is satisfied, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the first thin film layer is preferably 33 at% or more and 66 at% or less, More preferably, it is 40 at% or more and 57 at% or less.

[Production method of laminated film]
The laminated film can be produced by forming a thin film layer on the surface of the base material on the thin film layer forming side by a known method such as a plasma CVD method. Especially, it is preferable to form a thin film layer by a continuous film-forming process, and it is more preferable to form a thin film layer continuously on it, conveying a elongate base material continuously.

  When the thin film layer is formed (deposited) by plasma CVD, the substrate is placed on a pair of deposition rolls, and plasma CVD is performed to generate plasma by discharging between the pair of deposition rolls. It is preferable to form. Further, when discharging between the pair of film forming rolls in this way, it is preferable to reverse the polarities of the pair of film forming rolls alternately.

  When generating plasma in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rolls. A pair of film forming rolls is used, and a base material is provided for each of the pair of film forming rolls. More preferably, a plasma is generated by discharging between a pair of film forming rolls. In this way, a pair of film forming rolls is used, a base material is disposed on the pair of film forming rolls, and discharge is performed between the pair of film forming rolls. It is possible not only to form a thin film layer efficiently, but also to form a film on the surface portion of the base material existing on the other film forming roll at the same time. The film formation rate can be doubled. From the viewpoint of productivity, the thin film layer is preferably formed on the surface of the substrate by a roll-to-roll method. An apparatus that can be used when manufacturing a laminated film by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rolls and a plasma power source, and between the pair of film forming rolls. It is preferable that the apparatus has a configuration capable of discharging.

  As an example of a film forming apparatus applied to the roll-to-roll type plasma CVD method, a feed roll, a transport roll, a film forming roll, a transport roll, and a winding roll are sequentially formed from the film forming upstream side (the upstream side in the substrate transport direction). Examples include a take-up roll, a gas supply pipe, a power source for plasma generation, and a magnetic field generator. Among these, at least the film forming roll, the gas supply pipe, and the magnetic field generator are arranged in a vacuum chamber when the laminated film is manufactured, and this vacuum chamber is connected to a vacuum pump. The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

  The film forming apparatus preferably includes a pair of film forming rolls as a film forming roll, and further preferably includes a transport roll between these film forming rolls. And it is preferable that a magnetic field generator is disposed inside these film forming rolls, and these magnetic field generating apparatuses are mounted so that their postures do not change with the rotation of the film forming rolls.

  When such a film forming apparatus is used, the base material wound around the feed roll is transported from the feed roll to the upstream (upstream side) film forming roll via the most upstream transport roll. . And the film base material in which the thin film was formed on the surface of the base material is conveyed from the front | former film-forming roll to the back | latter stage (downstream side) film-forming roll via a conveyance roll. Further, the laminated film obtained by further forming a film to form a thin film layer is conveyed from a subsequent film-forming roll to a take-up roll via a further downstream (most downstream) conveyance roll. , And is wound on this winding roll.

  In the film forming apparatus, the pair of film forming rolls (the front stage and the rear stage) are arranged so as to face each other. The axes of these film forming rolls are substantially parallel, and the diameters of these film forming rolls are substantially the same. In such a film forming apparatus, film formation is performed when the base material is transported on the former film forming roll and when the film base material is transported on the subsequent film forming roll.

  In the film forming apparatus, plasma can be generated in a space between a pair of film forming rolls. The plasma generating power source is electrically connected to the electrodes in the film forming rolls, and these electrodes are arranged so as to sandwich the space.

  The film forming apparatus described above can generate plasma by the power supplied to the electrode from a plasma generation power source. As the plasma generating power source, a known power source or the like can be used as appropriate, and examples thereof include an AC power source capable of alternately reversing the polarities of the two electrodes. From the viewpoint of enabling efficient film formation, the power supply for plasma generation is set to, for example, 0.1 to 10 kW, and the AC frequency is set to, for example, 50 Hz to 100 MHz. An AC frequency set to 1 MHz to 100 MHz may be used from the viewpoint of increasing the decomposition efficiency of the source gas.

  The magnetic field generator arranged inside the film forming roll can generate a magnetic field in the space, and may generate the magnetic field so that the magnetic flux density changes in the transport direction on the film forming roll.

  The gas supply pipe can supply a supply gas used for forming the thin film layer to the space. The supply gas includes a raw material gas for the thin film layer. The source gas supplied from the gas supply pipe is decomposed by the plasma generated in the space, and a film component of the thin film layer is generated. The film component of the thin film layer is deposited on the substrate transported on the pair of film forming rolls or the film substrate.

  As the source gas, the thin film layer is formed using at least three kinds of gases of the first source gas, the second source gas, and the third source gas.

  An inorganic silane-based gas is used as the first source gas. Examples of such inorganic silane-based gases include monosilane gas, disilane gas, trisilane gas, dichlorosilane gas, trichlorosilane gas, and tetrachlorosilane gas. Among these inorganic silane-based gases, monosilane gas and disilane gas are preferable from the viewpoints of handling of compounds and denseness of the obtained thin film layer. Moreover, these inorganic silane-type gas can be used individually by 1 type or in combination of 2 or more types.

  When an organosilicon compound gas is used as the first source gas, the source material contains a large amount of C—H groups, so that the bond dissociation energy required for decomposing the source gas during plasma CVD film formation is a C—H group. Is large at 443 kJ / mol, it is considered that a large amount of C—H groups remain in the thin film, and fine voids are formed, resulting in low density. On the other hand, when an inorganic silane-based gas is used as the first source gas, the bond dissociation energy is 318 kJ / mol when the Si—H group is used, 326 kJ / mol when the Si—Si group is used, and 397 kJ when the Si—Cl group is used. / Mol, the binding energy is lower than that of the C—H group, and the source gas can be sufficiently decomposed, so that the denseness in the thin film is increased and fine voids and cracks are less likely to occur.

  Further, a hydrocarbon gas is used as the second source gas. Examples of such hydrocarbon gases include acetylene gas, ethylene gas, methane gas, and the like. Moreover, these hydrocarbon type gas can be used individually by 1 type or in combination of 2 or more types.

  Further, oxygen gas is used as the third source gas.

  In addition to the first, second, and third source gases, the source gas may contain a carbon oxide gas, a gas containing N atoms, an ozone gas, and the like. Examples of the carbon oxide gas include carbon monoxide gas and carbon dioxide gas. Nitrogen gas, ammonia gas, etc. are mentioned as gas containing N atom. Moreover, gas other than these source gases can be used individually by 1 type or in combination of 2 or more types. Moreover, in this invention, it is preferable not to contain the gas of an organosilicon compound from said viewpoint.

  The supply gas may contain at least one of a carrier gas and a discharge gas. As the carrier gas, a gas that promotes the supply of the source gas into the vacuum chamber can be appropriately selected and used. As the discharge gas, a gas that promotes the generation of plasma discharge in the space SP can be appropriately selected and used. Examples of the carrier gas and the discharge gas include rare gases such as helium gas, argon gas, neon gas, and xenon gas; oxygen gas; hydrogen gas. The carrier gas and the discharge gas can be used alone or in combination of two or more.

  In the film forming apparatus, the type of source gas, the ratio of the flow rates of three or more source gases, the power supplied to the electrodes, the pressure in the vacuum chamber, the diameter of the pair of film forming rolls, and the substrate (film substrate) By appropriately adjusting one or more parameters such as the transport speed of (), the average content of silicon atoms, oxygen atoms and carbon atoms in the thin film can be set to a desired amount. Note that one or more of the parameters may change over time within a period in which the substrate (film substrate) passes through the film formation area facing the space, or spatially within the film formation area. It may change.

  The electric power supplied to the electrode can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, and the like, and can be set to 0.1 to 10 kW, for example. The effect which suppresses generation | occurrence | production of a particle becomes high because electric power is 0.1 kW or more. Moreover, the effect which suppresses that a wrinkle and damage arise in a base material (film base material) with the heat | fever received from an electrode because electric power is 10 kW or less becomes high. Furthermore, it is possible to avoid occurrence of abnormal discharge between the pair of film forming rolls due to damage of the base material (film base material), and it is also possible to avoid damage to these film forming rolls due to abnormal discharge.

The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, and can be set to 0.1 Pa to 50 Pa, for example.
Although the conveyance speed (line speed) of a base material (film base material) can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., a base material is made to contact a conveyance roll as mentioned above. It is preferable that it is the same as the conveyance speed of a base material. The effect which suppresses that a wrinkle arises in a base material (film base material) because a conveyance speed is more than a lower limit becomes high.
Moreover, it becomes easy to increase the thickness of the thin film layer formed because a conveyance speed is below an upper limit.

  The film forming apparatus used for the production of the laminated film according to the present invention is not limited to the above-described one, and a part of the structure may be appropriately changed within a range not impairing the effects of the present invention.

  The laminated film according to the present invention may further include any one or more of a primer coat layer, a heat sealable resin layer, an adhesive layer, and the like, as necessary, in addition to the base material and the thin film layer. The primer coat layer can be formed using a known primer coat agent capable of improving the adhesion between the substrate and the thin film layer. Moreover, the said heat-sealable resin layer can be suitably formed using well-known heat-sealable resin. Moreover, the said adhesive bond layer can be suitably formed using a well-known adhesive agent, You may adhere several laminated | multilayer film with such an adhesive bond layer.

  Hereinafter, the present invention will be described in more detail based on examples.

[Example 1]
A biaxially stretched polyethylene terephthalate film (thickness: 100 μm) is used as a base material, and this is mounted on a feed roll. After evacuating the vacuum chamber for 12 hours, a thin film layer is formed. And while applying a magnetic field between a pair of film-forming rolls and supplying electric power to each of these film-forming rolls, discharge is generated between these film-forming rolls to generate plasma, and a film-forming gas ( Plasma CVD under the following film formation conditions by supplying monosilane gas as the first source gas, acetylene gas as the second source gas, and oxygen gas (which also functions as a discharge gas) as the third source gas) A thin film layer is formed by the method to obtain a laminated film.

<Film formation conditions>
Deposition roll width: 700mm
Deposition gas (mixed gas) supply amount: 10 to 10000 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
Pressure in the vacuum chamber: 0.1 to 10 Pa
Power supplied from the power source for plasma generation: 0.5 to 2.5 kW
Frequency of power source for plasma generation: 70 kHz
Substrate transport speed: 0.5 to 10 m / min

[Example 2]
A biaxially stretched polyethylene terephthalate film (thickness: 100 μm) is used as a base material, and this is mounted on a feed roll. After evacuating the vacuum chamber for 12 hours, a thin film layer is formed. And while applying a magnetic field between a pair of film-forming rolls and supplying electric power to each of these film-forming rolls, discharge is generated between these film-forming rolls to generate plasma, and a film-forming gas ( A gas mixture of disilane gas as the first source gas, acetylene gas as the second source gas, and oxygen gas (which also functions as a discharge gas) as the third source gas), and plasma CVD under the film forming conditions A thin film layer is formed by the method to obtain a laminated film.

[Example 3]
A biaxially stretched polyethylene terephthalate film (thickness: 100 μm) is used as a base material, and this is mounted on a feed roll. After evacuating the vacuum chamber for 12 hours, a thin film layer is formed. And while applying a magnetic field between a pair of film-forming rolls and supplying electric power to each of these film-forming rolls, discharge is generated between these film-forming rolls to generate plasma, and a film-forming gas ( A monosilane gas as a first source gas, an ethylene gas as a second source gas, and an oxygen gas (which also functions as a discharge gas) as a third source gas) and plasma CVD under the film formation conditions A thin film layer is formed by the method to obtain a laminated film.

  Since the laminated films obtained in Examples 1 to 3 all use inorganic silane-based gas, hydrocarbon-based gas, and oxygen gas as raw material gases, they are decomposed when a thin film layer is formed by plasma CVD. Since it is easy, it becomes a dense laminated film with few defects, and an industrially useful film is obtained.

Claims (7)

A laminated film comprising a substrate and a thin film layer formed on at least one surface of the substrate and containing a silicon atom, an oxygen atom and a carbon atom;
The thin film layer is formed by a plasma chemical vapor deposition method using a source gas containing an inorganic silane-based gas, a hydrocarbon-based gas, and an oxygen gas.   The laminated film according to claim 1, wherein the thin film layer is formed using a rare gas, an oxygen gas, or a mixture thereof as a discharge gas. In the thin film layer, the abundance ratio of silicon atoms (Si), oxygen atoms (O), and carbon atoms (C) is in the range of the following formulas (1) and (2): The laminated film according to any one of the above.
0.1 <C / Si <0.5 (1)
1.5 <O / Si <1.9 (2) The average density of the said thin film layer is 1.8 g / cm < ³ > or more, The laminated | multilayer film as described in any one of Claims 1-3 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 4, wherein a thin film layer is continuously formed on the base material while continuously conveying the long base material. the film. The distance from the surface of the thin film layer in the film thickness direction of the thin film layer, and the ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the barrier layer at the point located at the distance ( Silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship among silicon atom ratio), oxygen atom ratio (oxygen atom ratio), and carbon atom ratio (carbon atom ratio), respectively. In the following conditions (i) to (iii):
(I) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the following formula (3) in a region of 90% or more in the film thickness direction of the barrier layer. about,
(Oxygen atomic ratio)> (Si atomic ratio)> (Carbon atomic ratio) (3)
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve satisfies all that it is 5 at% or more. The laminated film as described.   The laminated film according to claim 1, wherein the source gas contains a carbon oxide.