JP2017053036A - Laminate film producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate film capable of suppressing the drop of a gas barrier sufficiently even in the case where the film is curved.SOLUTION: A laminate film comprises: a substrate; and at least one thin layer formed on the surface of said substrate. Said thin layer is a layer containing silica, oxygen and carbon, and a carbon distribution curve expressing a relation between a distance from the surface of said layer in the thickness direction of said layer, and a ratio (an atomic ratio of carbon), i.e., the quantity of carbon atoms against the total amount of the silicon atoms, the oxygen atoms and the carbon atoms of said layer satisfies all the following conditions (i) to (iii): (i) said carbon distribution curve is substantially continuous; (ii) in said carbon distribution curve, the atomic ratio of carbon is 1 at% or more in the entire region of the film thickness of said layer; and (iii) said carbon distribution curve has an inclined region, in which the atom ratio of carbon increases, and an inclined region, in which the atom ratio of carbon decreases.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminated film that can be suitably used for flexible lighting using organic electroluminescence elements (organic EL elements), organic thin film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

  The gas barrier film can be suitably used as a container suitable for packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, a gas barrier film formed by forming a thin film of an inorganic compound such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide on one surface of a base film such as a plastic film has been proposed. .

As a method for forming a thin film of an inorganic compound on the surface of a plastic substrate in this manner, a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method, an ion plating method, or a thermochemical vapor deposition method is used. Chemical vapor deposition (CVD) such as (thermal CVD) and plasma enhanced chemical vapor deposition is known.
Moreover, as a gas barrier film manufactured using such a film forming method, for example, in Japanese Patent Laid-Open No. 4-89236 (Patent Document 1), two layers formed by vapor deposition on the surface of a plastic substrate are disclosed. A gas barrier film provided with a laminated vapor deposition film layer composed of the above silicon oxide film is disclosed.

JP-A-4-89236

  However, the gas barrier film as described in Patent Document 1 is used as a gas barrier film for packaging articles that can be satisfied even if the gas barrier property of packaging containers such as foods and drinks, cosmetics, and detergents is relatively low. However, as a gas barrier film for packaging an electronic device such as an organic EL element or an organic thin film solar cell, it is not necessarily sufficient in terms of gas barrier properties. In addition, the gas barrier film described in Patent Document 1 has a problem that the gas barrier property against oxygen gas or water vapor is lowered when the film is bent, and flex resistance is required like a flexible liquid crystal display. The gas barrier film used in the display device is not necessarily sufficient in terms of gas barrier properties when the film is bent.

  The present invention has been made in view of the above-described problems of the prior art, has a sufficient gas barrier property, and can sufficiently suppress a decrease in gas barrier property even when the film is bent. An object of the present invention is to provide a laminated film.

  As a result of intensive studies to achieve the above object, the present inventors have found that a laminated film comprising a base material and at least one thin film layer formed on the surface of the base material is a film of the thin film layer. A carbon distribution curve showing the relationship between the distance from the surface of the thin film layer in the thickness direction and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the thin film layer satisfies a specific condition In order to complete the present invention, it is found that a laminated film having a sufficient gas barrier property and capable of sufficiently suppressing a decrease in gas barrier property even when the film is bent is obtained. It came.

That is, the laminated film of the present invention is a laminated film comprising a substrate and at least one thin film layer formed on the surface of the substrate,
The thin film layer is a layer containing silicon, oxygen and carbon, and
Carbon showing the relationship between the distance from the surface of the layer in the film thickness direction of the layer and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) in the layer The distribution curve includes a layer that satisfies all of the following conditions (i) to (iii).
(i) the carbon distribution curve is substantially continuous;
(ii) In the carbon distribution curve, the atomic ratio of carbon is 1 at% or more in the entire region of the thickness of the layer, and
(iii) The carbon distribution curve has a slope region in which the atomic ratio of carbon increases and a slope region in which the atomic ratio of carbon decreases.

  The above layer containing silicon, oxygen and carbon and satisfying the conditions (i) to (iii) of the carbon distribution curve may be referred to as “layer G” hereinafter. In the carbon distribution curve, “total amount of silicon atoms, oxygen atoms and carbon atoms” means the total number of silicon atoms, oxygen atoms and carbon atoms, and “amount of carbon atoms” means the number of carbon atoms. Means. The same applies to “amount of silicon atoms” and “amount of oxygen atoms” for a silicon distribution curve, an oxygen distribution curve, and an oxygen carbon distribution curve, which will be described later. The unit “at%” is an abbreviation for “atomic%”.

  In the laminated film of the present invention, it is preferable that the carbon distribution curve of the layer has a maximum value and a minimum value of the atomic ratio of carbon.

  In the laminated film of the present invention, it is also preferable that the carbon distribution curve of the layer has an extreme value of three or more of the atomic ratio of carbon.

  In the laminated film of the present invention, in the carbon distribution curve of the layer, the atomic ratio of carbon is preferably 5 at% or more over the entire film thickness direction of the layer.

  In the laminated film of the present invention, the distance from the surface of the layer in the film thickness direction of the layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer (silicon atoms) In the silicon distribution curve indicating the relationship between the maximum value of the atomic ratio of silicon and the minimum value of the minimum value of the atomic ratio of silicon is 5 at% or less. It is preferable.

  In the laminated film of the present invention, in the carbon distribution curve of the layer, the difference between the maximum value of the maximum value of the atomic ratio of carbon and the minimum value of the minimum value of the atomic ratio of carbon is It is preferable that it is 5 at% or more.

  In the laminated film of the present invention, in the carbon distribution curve of the layer, the atomic ratio of carbon is preferably 67 at% or less over the entire film thickness direction of the layer.

  In the laminated film of the present invention, the layer preferably contains a direct bond between a silicon atom and a carbon atom.

  Furthermore, in the laminated film of the present invention, the layer is preferably a thin film formed by a plasma chemical vapor deposition method using an organic silicon compound source gas and an oxygen gas as a film forming gas.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the laminated | multilayer film which has sufficient gas barrier property and can fully suppress the fall of gas barrier property, even when a film is bent.

It is a schematic diagram which shows an example of the manufacturing apparatus which can be used suitably for manufacturing the laminated | multilayer film of this invention. 2 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen-carbon distribution curve of a thin film layer of the laminated film obtained in Example 1. FIG. It is a ²⁹ Si-NMR spectrum of the material which had formed the thin film layer of the laminated | multilayer film obtained in Example 1. FIG. It is a ¹³ C-NMR spectrum of the material which has formed the thin film layer of the laminated film obtained in Example 1. It is a graph which shows the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve of the thin film layer of the laminated film obtained in Example 2. It is a graph which shows the element profile of the film thickness direction by the SIMS (secondary ion mass spectrometer) of the thin film layer of the laminated film obtained in Example 2. It is a graph which shows the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve of the thin film layer of the laminated film obtained in Example 3. It is a graph which shows the silicon concentration curve, oxygen concentration curve, and carbon concentration curve of the thin film layer of the laminated film obtained in Example 4. 3 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of a thin film layer of a laminated film obtained in Comparative Example 1. FIG. It is a graph which shows the element profile of the film thickness direction by SIMS (secondary ion mass spectrometer) of the thin film layer of the laminated | multilayer film obtained by the comparative example 1. FIG. It is a graph which shows the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve of the thin film layer of the laminated film obtained in Comparative Example 2.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

The laminated film of the present invention is a laminated film comprising a substrate and at least one thin film layer formed on the surface of the substrate,
The thin film layer is a layer containing silicon, oxygen and carbon, and
Carbon showing the relationship between the distance from the surface of the layer in the film thickness direction of the layer and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) in the layer The distribution curve includes a layer that satisfies all of the following conditions (i) to (iii).
(i) the carbon distribution curve is substantially continuous;
(ii) In the carbon distribution curve, the atomic ratio of carbon is 1 at% or more in the entire region of the film thickness of the layer,
(iii) In the carbon distribution curve, the atomic ratio of carbon has an increasing slope region and a decreasing slope region.

  Examples of the substrate used in the present invention include a film made of a resin. Examples of the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin. Among these resins, polyester resins and polyolefin resins are preferred, and PET and PEN are particularly preferred from the viewpoints of high heat resistance and linear expansion coefficient and low production cost. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the base material can be appropriately set in consideration of the transport of the base material and the stability of plasma discharge when the laminated film of the present invention is produced. The thickness of the substrate is preferably in the range of 5 to 500 μm from the viewpoint that the film can be conveyed even in a vacuum. Furthermore, when forming the thin film layer concerning this invention by plasma CVD method, since the thin film layer is formed while discharging through the base material, the thickness of the base material is more preferably in the range of 50 to 200 μm. A range of 50 to 100 μm is particularly preferable.

  Moreover, it is preferable to perform the surface activation process for activating the surface of a base material to the said base material from an adhesive viewpoint with the thin film layer mentioned later. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

  The thin film layer concerning this invention is formed in the at least single side | surface of the said base material. And in the laminated | multilayer film of this invention, it is necessary for the said thin film layer to contain the layer containing silicon, oxygen, and carbon. The layer containing silicon, oxygen and carbon may further contain nitrogen and aluminum.

  In the present invention, the carbon distribution curve of the layer containing silicon, oxygen and carbon satisfies all of the above conditions (i) to (iii). As described above, the above layer containing silicon, oxygen, and carbon and satisfying the conditions (i) to (iii) of the carbon distribution curve may be hereinafter referred to as “layer G”. That is, the layer G first has a surface in the film thickness direction of the layer G (if the thin film layer or the like is further laminated on the layer G, the interface with the upper layer of the layer G is And (i) the carbon distribution curve showing the relationship between the distance from the point) and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer G (atomic ratio of carbon). It is necessary that the distribution curve is substantially continuous. Since the carbon is distributed so that the carbon distribution curve is substantially continuous, the film has excellent gas barrier properties when the film is bent.

In the present specification, “the carbon distribution curve is substantially continuous” means that the carbon atomic ratio in the carbon distribution curve does not include a portion that changes discontinuously, specifically, In the relationship between the distance from the surface of the layer G in the film thickness direction of the layer G (x, unit: nm) and the atomic ratio of carbon (C, unit: at%), the following mathematical formula (F1):
| dC / dx | ≦ 1 (F1)
This means that the condition represented by

  Further, such a layer G has (ii) the carbon distribution curve in which the atomic ratio of carbon is 1 at% or more in the entire region of the film thickness of the layer G, that is, the film thickness of the layer G In all regions, the minimum value of the atomic ratio of carbon needs to be 1 at% or more. When the layer G includes a region containing almost no carbon atoms or an inorganic region containing no carbon atoms, the gas barrier property when the film of the laminated film is bent is insufficient. In such a layer G, the carbon atomic ratio is preferably 5 at% or more in the entire region of the film thickness. As for the upper limit of the carbon atomic ratio, the carbon atomic ratio in the carbon distribution curve is preferably 67 at% or less in the entire region of the film thickness.

  The carbon atom contained in the layer G is a carbon atom bonded to at least one hydrogen atom, that is, an organic carbon atom. That is, in the layer G according to the present invention, the entire region of the layer thickness is an organic region. In the present specification, the organic substance region means a region containing a carbon-hydrogen bond. In the present invention, since the organic carbon is contained in the entire region of the thickness of the layer G, a thin film layer having excellent flexibility is obtained, and a laminated film having excellent gas barrier properties when the film is bent is obtained. Can be obtained.

  Further, such a layer G needs to further include (iii) a slope region in which the atomic ratio of carbon increases and a slope region in which the atomic ratio of carbon decreases in the carbon distribution curve. When the carbon distribution curve has only one of the increasing slope region and the decreasing slope region, or when it has none (when the carbon atoms are uniformly distributed in the layer G), When the film of the laminated film is bent, the gas barrier property becomes insufficient.

  The carbon distribution curve preferably has at least one extreme value with respect to the atomic ratio of carbon. In such a layer G, the carbon distribution curve more preferably has at least two extreme values with respect to the atomic ratio of carbon, and particularly preferably has at least three extreme values. When the carbon distribution curve has an extreme value, the gas barrier property when the film of the laminated film is bent becomes better. In addition, when the carbon distribution curve has at least three extreme values as described above, the layer in the film thickness direction of the layer G at one extreme value and the extreme value adjacent to the extreme value of the carbon distribution curve. The absolute value of the difference in distance from the surface of G is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the extreme value means the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the thin film layer in the film thickness direction of the thin film layer. In the present invention, the maximum value is a point in the element distribution curve where the atomic ratio value of the element changes from increasing to decreasing with a continuous change in the distance from the surface of the thin film layer. The value of the atomic ratio of the element at a position where the distance from the surface of the thin film layer in the film thickness direction of the thin film layer is further changed by 20 nm than the value of the atomic ratio of the element is reduced by 3 at% or more. Say. Further, in the present invention, the minimum value is a point in the element distribution curve where the value of the atomic ratio of the element changes from decreasing to increasing as the distance from the surface of the thin film layer continuously changes. The value of the atomic ratio of the element at a position where the distance from the surface of the thin film layer in the film thickness direction of the thin film layer is further changed by 20 nm than the value of the atomic ratio of the element is increased by 3 at% or more. Say.

  In such a layer G, the difference (absolute value) between the maximum value of the maximum value and the minimum value of the minimum value of the carbon distribution curve is preferably 5 at% or more. In such a layer G, the absolute value of the difference between the maximum value of the maximum value of the carbon atomic ratio and the minimum value of the minimum value is more preferably 6 at% or more, and 7 at% or more. It is particularly preferred that When the absolute value is 5 at% or more, the gas barrier property is improved when the laminated film is bent.

  In the present invention, the distance from the surface of the layer G in the film thickness direction of the layer G and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer (atomic ratio of oxygen) It is preferable that the oxygen distribution curve showing the relationship with () has at least one extreme value, more preferably at least two extreme values, and particularly preferably at least three extreme values. When the oxygen distribution curve does not have an extreme value, the gas barrier property tends to decrease when the laminated film is bent. In the case where the oxygen distribution curve has at least three extreme values as described above, the one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value in the film thickness direction of the thin film layer. The absolute value of the difference in distance from the surface of the thin film layer is preferably 200 nm or less, and more preferably 100 nm or less.

  In the present invention, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the layer G is preferably 5 at% or more, more preferably 6 at% or more, and 7 at % Or more is particularly preferable. When the absolute value is less than the lower limit, gas barrier properties tend to be lowered when the laminated film is bent.

  In the present invention, the distance from the surface of the layer G in the thickness direction of the layer G and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer (atom ratio of silicon) In the silicon distribution curve showing the relationship between the maximum value and the minimum value of the minimum value of the silicon distribution curve, the difference (absolute value) is preferably 5 at% or less. % Is more preferable, and it is particularly preferable that it is less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier property of the laminated film tends to be lowered.

  In the present invention, the distance from the surface of the layer in the film thickness direction of the layer G and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer (oxygen) And the oxygen carbon distribution curve showing the relationship with the atomic ratio of carbon), the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen carbon distribution curve is less than 5 at%. Preferably, it is less than 4 at%, more preferably less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier property of the laminated film tends to be lowered.

In the present invention, as shown in the following formula, in the silicon distribution curve, the atomic ratio of silicon is 90% or more (more preferably 95% or more, particularly preferably 100%) of the thickness of the layer G. Is preferably 30.0 at% or more and 37.0 at% or less. When the atomic ratio of silicon is within the range, the gas barrier property when the laminated film is bent is improved.
30at% ≦ (amount of silicon atom) / {(amount of oxygen atom) + (amount of carbon atom) + (amount of silicon atom)} ≦ 37at%

In the present invention, in the layer G, as shown in the following formula, the ratio of the total amount of oxygen atoms and carbon atoms to the number of silicon atoms is greater than 1.8 and not greater than 2.2. It is preferable. When this ratio is within the range, the gas barrier property when the film of the laminated film is bent becomes better.
1.8 <{(amount of oxygen atoms) + (amount of carbon atoms)} / (amount of silicon atoms) ≦ 2.2

In the present invention, in the region of 90% or more (more preferably 95% or more, particularly preferably 100%) of the thickness of the layer G, the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are as follows: It is preferable that the condition represented by the formula (1) or the following formula (2) is satisfied. When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the above conditions, the gas barrier property of the laminated film becomes better.
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the above formula (1 ), The atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer G is preferably 25 to 45 at%, More preferably, it is ˜40 at%. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer G is preferably 33 to 67 at%, more preferably 45 to 67 at%. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer G is preferably 3 to 33 at%, and more preferably 3 to 25 at%.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the above formula (2 ), The atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer G is preferably 25 to 45 at%, More preferably, it is ˜40 at%. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer G is preferably 1 to 33 at%, and more preferably 10 to 27 at%. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer G is preferably 33 to 66 at%, and more preferably 40 to 57 at%.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and ion sputtering of a rare gas such as argon. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the thin film layer in the film thickness direction of the thin film layer in the film thickness direction. As the distance from the surface of the thin film layer in the film thickness direction of the thin film layer, the distance from the surface of the thin film layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement may be adopted. it can. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  In the present invention, in such a layer G, it is preferable that carbon atoms are directly bonded to silicon atoms. In the layer G, since the direct bond is included between the silicon atom and the carbon atom, the gas barrier property when the film of the laminated film is bent is further improved.

  In the present invention, the layer G is substantially in the film surface direction (direction parallel to the surface of the thin film layer) from the viewpoint of forming a thin film layer having a uniform and excellent gas barrier property over the entire film surface. Preferably it is uniform. In this specification, the layer G is substantially uniform in the film surface direction means that the oxygen distribution curve, the carbon distribution curve, and the carbon distribution curve at any two measurement points on the film surface of the layer G by XPS depth profile measurement. When an oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the maximum and minimum values of the carbon atomic ratio in each carbon distribution curve The absolute value of the difference between the values is the same as each other or within 5 at%.

  The thickness of the layer G is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. If the thickness of the layer G is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the thickness exceeds the upper limit, the gas barrier properties tend to decrease due to bending.

  The laminated film of the present invention needs to include at least one layer G that satisfies all of the above conditions (i) to (iii), but may include two or more layers that satisfy such conditions. Further, when two or more such thin film layers are provided, the materials of the plurality of thin film layers may be the same or different. When two or more such thin film layers are provided, such a thin film layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Further, the plurality of thin film layers including such a layer G may include a thin film layer that does not necessarily have a gas barrier property.

  When the laminated film of the present invention includes a plurality of thin film layers, the total thickness of the thin film layers is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 5000 nm, and preferably in the range of 100 to 3000 nm. Is more preferable, and the range of 200 to 2000 nm is particularly preferable. If the total thickness of the thin film layer is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the upper limit is exceeded, the gas barrier properties tend to decrease due to bending. .

  The laminated film of the present invention includes the base material and the thin film layer, but may further include a primer coat layer, a heat sealable resin layer, an adhesive layer, and the like as necessary. Such a 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, such a heat-sealable resin layer can be suitably formed using a well-known heat-sealable resin. Furthermore, such an adhesive layer can be appropriately formed using a known adhesive, and a plurality of laminated films may be bonded to each other by such an adhesive layer.

  In the laminated film of the present invention, the thin film layer is preferably a layer formed by a plasma chemical vapor deposition method. As a thin film layer formed by such a plasma chemical vapor deposition method, plasma chemistry in which the base material is disposed on the pair of film forming rolls and plasma is generated by discharging between the pair of film forming rolls. A layer formed by a vapor deposition method is more preferable. 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. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a gas containing an organic silicon compound source gas and an oxygen gas is preferable, and the oxygen content in the film forming gas is determined by the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount required for complete oxidation of the total amount of the organosilicon compound in the gas. Moreover, in the laminated | multilayer film of this invention, it is preferable that the said thin film layer is a layer formed of the continuous film-forming process. In addition, the method of forming a thin film layer using such a plasma chemical vapor deposition method is demonstrated in the method of manufacturing the laminated film of this invention mentioned later.

  Next, a method for producing the laminated film of the present invention will be described. The laminated film of the present invention can be produced by forming the thin film layer on the surface of the substrate. As a method of forming such a thin film layer according to the present invention on the surface of the substrate, it is preferable to employ plasma chemical vapor deposition (plasma CVD) from the viewpoint of gas barrier properties.

  Further, when generating plasma in the plasma enhanced chemical vapor deposition method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rolls, and a pair of film forming rolls is used, and the pair of film forming films is used. More preferably, the substrate is disposed on each of the rolls, and plasma is generated by discharging between the pair of film forming rolls. In this way, a pair of film forming rolls are 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 film on the surface part of the base material existing in the film, but also to form a film on the surface part of the base material existing on the other film forming roll at the same time. The film formation rate can be doubled and a film having the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled, and the layer efficiently satisfies all the above conditions (i) to (iii) Can be formed. Moreover, it is preferable that the laminated film of this invention forms the said thin film layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. Further, an apparatus that can be used when producing a laminated film by such a plasma chemical vapor deposition method is not particularly limited, and includes at least a pair of film forming rolls and a plasma power source, It is preferable that the apparatus has a configuration capable of discharging between the film forming rolls. For example, when the manufacturing apparatus shown in FIG. 1 is used, roll-to-roll using plasma chemical vapor deposition is used. It becomes possible to manufacture by a roll system.

  Hereinafter, the method for producing the laminated film of the present invention will be described in more detail with reference to FIG. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the laminated film of the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

First, definitions of main terms or expressions used in the following description are given. In addition, the following definitions are applied also to description before this.
A “vacuum chamber” is a container for evacuating the interior. Normally, a vacuum environment is created in the chamber by operating a vacuum pump attached to the chamber.
The “substrate” is an object that becomes a support for the film when the film is formed.
The “film-forming roll” is a roll for forming a film on the surface of the substrate wound around it, and is usually made of metal and also serves as an electrode for discharge. Note that “wrapping” means bringing a bendable object such as a film into contact with a cylindrical object such as a roll so as to cover the cylindrical object.
An “organosilicon compound” is an organic compound containing silicon as a constituent element.
“Film-forming gas” is a gas containing a raw material gas that is a raw material of a film as an essential element, and if necessary, a reactive gas that reacts with the raw material gas to form a compound, or is included in the formed film In some cases, it may further contain an auxiliary gas that contributes to plasma generation and film quality improvement.
The “source gas” is a gas that is a supply source of a material that is a main component of the film. For example, when an SiO _x film is formed, a gas containing Si such as HMDSO, TEOS, silane or the like is a source gas.
The “reactive gas” is a gas that reacts with the raw material gas and is taken into the formed film. For example, when forming a SiO _x film, oxygen (O ₂ ) corresponds to this.
The “magnetic field generating member” is a magnetic field generating mechanism composed of a permanent magnet, for example, a member composed of a long central magnet, an outer peripheral magnet surrounding the central magnet, and a magnetic field short-circuiting member connecting them. .
The “plasma power source” is a power source that is connected to a pair of film forming rolls that are electrodes and generates plasma between the film forming rolls. “Plasma generating power source” is also synonymous.
“0 ° C., 1 atm reference” indicates that the amount of gas displayed is the volume of the gas at 0 ° C., 1 atm.
“To completely oxidize an organosilicon compound” means that an organosilicon compound contains Si, C and H contained in the compound, Si becomes SiO ₂ , C becomes CO ₂ , and H becomes H ₂ O. Means to be oxidized.

  1 includes a feed roll 11, transport rolls 21, 22, 23, 24, film forming rolls 31, 32, a gas supply pipe 41, a plasma generating power supply 51, a film forming roll 31, and 32 includes magnetic field generators 61 and 62 installed inside 32, and a winding roll 71. In such a manufacturing apparatus, at least the film forming rolls 31, 32, the gas supply pipe 41, the plasma generating power source 51, and the magnetic field generating apparatuses 61, 62 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roll has a plasma generation power source so that the pair of film-forming rolls (film-forming roll 31 and film-forming roll 32) can function as a pair of counter electrodes. 51 is connected. Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roll 31 and the film forming roll 32 by supplying power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roll 31 and the film forming roll 32. In this way, when the film forming roll 31 and the film forming roll 32 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable that the pair of film forming rolls (film forming rolls 31 and 32) are arranged so that their central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rolls (film forming rolls 31 and 32), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form a thin film layer on the surface of the film 100 by the CVD method, while depositing a film component on the surface of the film 100 on the film forming roll 31, Furthermore, since the film component can be deposited on the surface of the film 100 also on the film forming roll 32, the thin film layer can be efficiently formed on the surface of the film 100.

  Further, inside the film forming roll 31 and the film forming roll 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roll rotates are provided, respectively.

  Further, as the film forming roll 31 and the film forming roll 32, known rolls can be appropriately used. As such film forming rolls 31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rolls 31 and 32 is preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in such a manufacturing apparatus, the film 100 is arrange | positioned on a pair of film-forming roll (The film-forming roll 31 and the film-forming roll 32) so that the surface of the film 100 may oppose, respectively. By disposing the film 100 in this manner, each of the films 100 existing between the pair of film forming rolls is generated when the plasma is generated by performing discharge between the film forming roll 31 and the film forming roll 32. It becomes possible to form a film on the surface simultaneously. That is, according to such a manufacturing apparatus, the film component can be deposited on the surface of the film 100 on the film forming roll 31 and further the film component can be deposited on the film forming roll 32 by the CVD method. Therefore, the thin film layer can be efficiently formed on the surface of the film 100.

  Further, as the feed roll 11 and the transport rolls 21, 22, 23, and 24 used in such a manufacturing apparatus, known rolls can be appropriately used. Further, the winding roll 71 is not particularly limited as long as it can wind the film 100 on which the thin film layer is formed, and a known roll can be appropriately used.

  Further, as the gas supply pipe 41, a pipe capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used. Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roll 31 and the film forming roll 32 connected to the power source 51 and makes it possible to use them as a counter electrode for discharging. As such a plasma generation power source 51, it is possible to more efficiently carry out plasma CVD, so that the polarity of the pair of film forming rolls can be alternately reversed (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 51 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate. Furthermore, as the film 100, in addition to the base material used in the present invention, a film in which the thin film layer is formed in advance can be used. As described above, by using the film 100 in which the thin film layer is formed in advance, it is possible to increase the thickness of the thin film layer.

  Using the manufacturing apparatus shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roll, and the film transport speed are adjusted as appropriate. By doing so, the laminated film of the present invention can be produced. That is, by using the manufacturing apparatus shown in FIG. 1 to generate a discharge between a pair of film forming rolls (film forming rolls 31 and 32) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. The film forming gas (raw material gas or the like) is decomposed by plasma, and the thin film layer is formed on the surface of the film 100 on the film forming roll 31 and on the surface of the film 100 on the film forming roll 32 by the plasma CVD method. Is done. In such film formation, the film 100 is conveyed by the delivery roll 11, the film formation roll 31, and the like, respectively, so that the film 100 is formed on the surface of the film 100 by a roll-to-roll continuous film formation process. A thin film layer is formed.

  The source gas in the film-forming gas used for forming such a thin film layer can be appropriately selected and used according to the material of the thin film layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of properties such as handling of the compound and gas barrier properties of the obtained thin film layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types. Furthermore, as a source gas, in addition to the above-mentioned organosilicon compound, monosilane may be contained and used as a silicon source for a thin film layer to be formed.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, a thin film that satisfies all the above conditions (i) to (iii) cannot be obtained. In this case, excellent barrier properties and bending resistance cannot be obtained depending on the formed thin film layer. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, a film containing hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O) as a raw material gas and oxygen (O ₂ ) as a reaction gas is used as the film forming gas. -Taking the case of producing an oxygen-based thin film as an example, the preferred ratio of the source gas to the reaction gas in the film-forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material. When producing a thin film, the following reaction formula (1) is given by the film-forming gas:
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
Reaction occurs as described in 1 to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. ) To (iii) cannot be formed. Therefore, in the present invention, when forming the thin film layer, the oxygen amount is set to the stoichiometric ratio with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above formula (1) does not proceed completely. It is desirable to have less than 12 moles. Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is the raw material hexamethyldisiloxane. (It may be about 20 times or more of the molar amount (flow rate).) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the thin film layer, and the above conditions (i) to (iii) It is possible to form a thin film layer satisfying all of the above), and to exhibit excellent barrier properties and bending resistance in the obtained laminated film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, carbon atoms and hydrogen atoms that have not been oxidized are excessively taken into the thin film layer. In this case, the transparency of the barrier film decreases, and the barrier film cannot be used for a flexible substrate for a device that requires transparency such as an organic EL device or an organic thin film solar cell. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.1 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming rolls 31 and 32, an electrode drum connected to the plasma generating power source 51 (in this example, installed on the film forming rolls 31 and 32). .) Can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but is preferably in the range of 0.1 to 10 kW. . If this applied power is less than the lower limit, particles tend to be generated.On the other hand, if the upper limit is exceeded, the amount of heat generated during film formation increases, and the temperature of the substrate surface during film formation increases. If the substrate loses heat and wrinkles occur during film formation, or if it is severe, the film melts due to heat and a large current discharge occurs between the bare film formation rolls, damaging the film formation roll itself. There is a possibility that

  The conveyance speed (line speed) of the film 100 can be adjusted as appropriate according to the type of raw material gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.1 to 100 m / min. A range of 5 to 20 m / min is more preferable. If the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film. On the other hand, if the upper limit is exceeded, the thickness of the formed thin film layer tends to be thin.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the water vapor permeability of the laminated film and the water vapor permeability after the bending test were measured by the following methods.

(I) Measurement of water vapor permeability Under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side, a water vapor permeability measuring device (model name “GTR Tech− 30XASC ") was used to measure the water vapor permeability of the laminated film. In addition, using a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. The water vapor permeability of the laminated film was measured.

(Ii) Measurement of water vapor permeability after bending test After winding a laminated film around a metal rod, a bending test was conducted for 1 minute, and then the laminated film was returned to a flat state to prepare a sample. The radius of curvature R in the bending test corresponds to ½ of the diameter of the rod. However, when the number of windings of the laminated film increases, ½ of the diameter when the film is wound is defined as the radius of curvature R. Next, a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) is used under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. Then, the water vapor permeability of the sample was measured.

Example 1
A laminated film was produced using the production apparatus shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) is used as a base material (film 100 in FIG. 1). It was attached to Le 11. And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to the film-forming roll 31 and the film-forming roll 32, respectively, In this discharge region, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a reactive gas) is generated in such a discharge region. And a thin film was formed by plasma CVD under the following conditions to obtain a laminated film.

<Film formation conditions>
Supply amount of source gas: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C., 1 atm standard)
Oxygen gas supply amount: 500 sccm (0 ° C., 1 atm standard)
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

The thickness of the thin film layer in the obtained laminated film was 0.3 μm. Further, the water vapor permeability of the obtained laminated film under conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side and a humidity of 90% RH on the high humidity side is 3.1 × 10 ⁻⁴ g / (m ² · day), and the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit. Furthermore, the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. Thus, it was confirmed that even when the obtained laminated film was bent, the gas barrier property could be sufficiently suppressed.

Moreover, about the obtained laminated | multilayer film, XPS depth profile measurement was performed on the following conditions, and the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve were obtained.
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 “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

  FIG. 2 shows a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve in which the vertical axis represents the atomic concentration (atomic ratio) (%) and the horizontal axis represents the sputtering time (minutes). FIG. 2 also shows the relationship between the concentration of each atom of silicon, oxygen, and carbon and the distance (nm) from the surface of the thin film layer. The “distance (nm)” shown on the horizontal axis of the graph shown in FIG. 2 is a value calculated from the sputtering time and the sputtering speed.

  As apparent from the results shown in FIG. 2, the obtained carbon distribution curve is substantially continuous, the thin film layer contains 1 at% or more of carbon throughout the thickness direction of the film, and the entire film is made of organic matter. It was a gas barrier film. It was also confirmed that there are many inclined regions where the atomic ratio of carbon increases and inclined regions where the atomic ratio of carbon decreases in the film thickness direction of the carbon distribution curve.

Then, the powder of the material which had formed the thin film layer was obtained by peeling only the part formed into a film from the PEN base material of the obtained laminated | multilayer film. The powder was collected and placed in a solid NMR sample tube and subjected to ²⁹ Si solid NMR to obtain a spectrum. FIG. 3 shows a ²⁹ Si-NMR spectrum. In the spectrum, there was an NMR peak in which the organic functional group R was bonded to a silicon atom, so that the thin film layer contained a direct bond between the silicon atom and the organic carbon atom. It was confirmed that

FIG. 4 shows a ¹³ C-NMR spectrum of the powder. In the spectrum, among the broad peaks of various organic substances, the peak of Si—CH ₃ (0 ppm) is particularly steep, and the thin film layer has a structure in which a methyl group is bonded to a silicon atom. It was also confirmed that many were included.

(Example 2)
First, except that the laminated film having a thickness of 0.3 μm obtained in Example 1 was attached to the roll 11 as a film 100 and a thin film layer was newly formed on the surface of the thin film layer, In the same manner as in Example 1, a laminated film (A) was obtained. In addition, the thickness of the thin film layer on the base material (PEN film) in the obtained laminated film (A) was 0.6 μm.

  Thereafter, the laminated film (A) obtained was attached to the delivery roll 11 as a film 100 and a thin film layer was newly formed in the same manner as in Example 1 except that a thin film layer was newly formed on the surface of the thin film layer. B) was obtained.

The thickness of the thin film layer in the obtained laminated film (B) was 0.9 μm. Further, the water vapor permeability of the obtained laminated film (B) under the conditions of a temperature of 40 ° C., a low humidity side humidity of 0% RH and a high humidity side humidity of 90% RH is 6.9 × 10 ⁻⁴ g / ( m ² · day), and the water vapor permeability of the laminated film under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit. Furthermore, the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. Thus, it was confirmed that even when the obtained laminated film (B) is bent, the gas barrier property can be sufficiently suppressed.

  About the thin film layer of the obtained gas-barrier laminated film (B), a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen-carbon distribution curve were prepared by the same method as in Example 1. Further, regarding the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve, a graph showing the relationship between the atomic ratio and the etching time as well as the relationship between the atomic ratio and the distance (nm) from the surface of the thin film layer. Is shown in FIG. Note that “distance (nm)” described on the horizontal axis of the graph of FIG. 5 is a value calculated from the etching time and the etching rate.

  As is apparent from the results shown in FIG. 5, the obtained carbon distribution curve is substantially continuous and contains 1 at% or more of carbon throughout the thickness direction of the film, and the entire film is an organic gas barrier film. It was. It was also confirmed that there are many inclined regions where the atomic ratio of carbon increases and inclined regions where the atomic ratio of carbon decreases in the film thickness direction of the carbon distribution curve. Furthermore, in the thin film layer, it was confirmed that the ratio of the total amount of oxygen atoms and carbon atoms to the amount of silicon atoms was greater than 1.8 and not greater than 2.2.

  In FIG. 6, the element profile of the film thickness direction by SIMS (secondary ion mass spectrometer) of the obtained laminated | multilayer film is shown. The concentration distribution profile of carbon atoms and the concentration distribution profile of hydrogen atoms are highly correlated, and carbon atoms are present with hydrogen atoms in the thin film layer of the laminated film, that is, carbon atoms are organic carbon. It was confirmed to exist as an atom.

(Example 3)
A laminated film was obtained in the same manner as in Example 1 except that the supply amount of the source gas was set to 100 sccm (0 ° C., 1 atm standard).

The thickness of the thin film layer in the obtained laminated film was 0.6 μm. Further, the water vapor permeability of the obtained laminated film under conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side and a humidity of 90% RH on the high humidity side is 3.2 × 10 ⁻⁴ g / (m ² · day), and the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit. Furthermore, the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. Thus, it was confirmed that even when the obtained laminated film was bent, the gas barrier property could be sufficiently suppressed.

  Moreover, about the obtained laminated | multilayer film, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve were created by the method similar to the method in Example 1. FIG. The obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve are shown in FIG. “Distance (nm)” indicated on the horizontal axis of the graph of FIG. 7 is a value calculated from the sputtering time and the sputtering speed.

  As is apparent from the results shown in FIG. 7, the obtained carbon distribution curve is substantially continuous and contains 1 at% or more of carbon throughout the thickness direction of the film, and the entire film is an organic gas barrier film. It was. It was also confirmed that there are many inclined regions where the atomic ratio of carbon increases and inclined regions where the atomic ratio of carbon decreases in the film thickness direction of the carbon distribution curve.

Example 4
The same procedure as in Example 1 except that the supply amount of the source gas was 100 sccm (0 ° C., 1 atm reference), the oxygen gas supply amount was 50 sccm (0 ° C., 1 atm reference), and the pressure was 1.5 Pa. A laminated film was obtained.

The resulting laminated film has a water vapor transmission rate of 5 × 10 ⁻⁴ g / (m ² · day) under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side. The water vapor permeability of this laminated film was below the detection limit under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. Furthermore, the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. Thus, it was confirmed that even when the obtained laminated film was bent, the gas barrier property could be sufficiently suppressed.

  The obtained laminated film was subjected to XPS depth profile measurement in the same manner as in Example 1, and the carbon atomic ratio, silicon atomic ratio, and oxygen atomic ratio in the film thickness direction of the thin film were measured. The obtained silicon concentration curve, oxygen concentration curve, and carbon concentration curve are shown in FIG. The “distance (nm)” indicated on the horizontal axis of the graph of FIG. 8 is a value calculated from the sputtering time and the sputtering speed.

  As is clear from the results shown in FIG. 8, the carbon concentration curve in the film thickness direction of the thin film of the obtained laminated film is substantially continuous and contains 1 at% or more of carbon throughout the film thickness direction. The whole film was an organic gas barrier film. It was also confirmed that there are many inclined regions where the atomic ratio of carbon increases and inclined regions where the atomic ratio of carbon decreases in the thickness direction of the film. Furthermore, in almost all regions in the film thickness direction, the atomic ratio of carbon, the atomic ratio of silicon, and the atomic ratio of oxygen were (carbon atomic ratio)> (silicon atomic ratio)> (oxygen atomic ratio). .

(Comparative Example 1)
On the surface of a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”), using a silicon target, in an oxygen-containing gas atmosphere, A thin film layer made of silicon oxide was formed by a reactive sputtering method to obtain a laminated film for comparison.

The thickness of the thin film layer in the obtained laminated film was 100 nm. The obtained laminated film has a water vapor permeability of 1.3 g / (m ² · day) under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side, and has a gas barrier property. Was insufficient.

  About the obtained gas barrier property laminated film, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve were prepared by the same method as the method in Example 1. Furthermore, regarding the obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve, the relationship between the atomic ratio and the distance (nm) from the surface of the thin film layer as well as the relationship between the atomic ratio and the etching time are combined. A graph shown in FIG. 9 is shown. Note that “distance (nm)” shown on the horizontal axis of the graph of FIG. 9 is a value calculated from the etching time and the etching rate. As is clear from the results shown in FIG. 9, the obtained carbon distribution curve confirms that the region where carbon is less than 1 at% occupies most of the film, and the whole is an inorganic film containing no carbon. It was done.

  In FIG. 10, the element profile of the film thickness direction by SIMS of the obtained laminated | multilayer film is shown. As shown in FIG. 10, the concentration distribution profile of carbon atoms and the concentration distribution profile of hydrogen atoms are both at the background level, and neither carbon atoms nor hydrogen atoms are present in the thin film layer of the laminated film. The thin film was confirmed to be an inorganic film consisting only of silicon atoms and oxygen atoms.

(Comparative Example 2)
A laminated film for comparison was obtained in the same manner as in Example 1 except that the supply amount of the source gas was 25 sccm (0 ° C., 1 atm standard).

The thickness of the thin film layer in the obtained laminated film was 0.2 μm. Further, the water vapor permeability of the obtained laminated film under conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side and a humidity of 90% RH on the high humidity side is 7.5 × 10 ⁻³ g / (m ² · day), and the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit. Further, the water vapor permeability of this laminated film under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is 2.7 × 10. ⁻¹ g / (m ² · day), and the gas barrier property was insufficient.

  About the obtained laminated | multilayer film, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve were created by the method similar to the method in Example 1. FIG. The obtained silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen-carbon distribution curve are shown in FIG. “Distance (nm)” described on the horizontal axis of the graph of FIG. 11 is a value calculated from the sputtering time and the sputtering speed. As is clear from the results shown in FIG. 11, the obtained carbon distribution curve shows that the carbon is less than 1 at%, there are many inorganic regions that do not contain carbon, and the inorganic region layer and the organic region layer alternate. It was confirmed that the entire film was not an organic gas barrier film but a mixture of an organic substance and an inorganic substance.

  As described above, the present invention provides a laminated film film that has a sufficient gas barrier property and can sufficiently suppress a decrease in gas barrier property even when the film is bent.

  Therefore, the laminated film film of the present invention can be suitably used for organic electroluminescence elements (organic EL elements), flexible lighting using organic EL elements, organic thin film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

  DESCRIPTION OF SYMBOLS 11 ... Sending roll, 21, 22, 23, 24 ... Conveyance roll, 31, 32 ... Film-forming roll, 41 ... Gas supply pipe, 51 ... Power source for plasma generation, 61, 62 ... Magnetic field generator, 71 ... Winding roll , 100 ... film.

Claims (1)

A method for producing a laminated film comprising a substrate and at least one thin film layer formed on the surface of the substrate,
In the thin film layer, the base material is disposed on a pair of film forming rolls, and a raw material gas and a reactive gas are supplied at a predetermined speed, and plasma is generated by discharging between the pair of film forming rolls. Formed by vapor deposition,
The thin film layer is a layer containing silicon, oxygen and carbon, and
Carbon distribution showing the relationship between the distance from the surface of the layer in the thickness direction of the layer and the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (carbon atomic ratio) of the layer The curve includes a layer that satisfies all of the following conditions (i) to (iii):
The layer comprises a direct bond of silicon and carbon atoms;
In the layer, silicon showing the relationship between the distance from the surface of the layer in the film thickness direction of the layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon) In the distribution curve, the difference between the maximum value of the maximum value of the silicon distribution curve and the minimum value of the minimum value is 5 at% or less,
A method for producing a laminated film in which the carbon distribution curve of the layer has three or more extreme values:
(i) the carbon distribution curve is substantially continuous;
(ii) In the carbon distribution curve, the atomic ratio of carbon is 1 at% or more in the entire region of the film thickness of the layer, and
(iii) The carbon distribution curve has a slope region where the carbon atomic ratio increases and a slope region where the carbon atomic ratio decreases.

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