JP2009097062A - Method for manufacturing gas-barrier film, manufacturing apparatus, and gas-barrier film obtained by the manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a gas-barrier film which realizes high gas barrier properties and simultaneously secures flexibility; a manufacturing apparatus therefor; and a gas-barrier film obtained by the manufacturing method or the manufacturing apparatus. <P>SOLUTION: The manufacturing method includes a vacuum step, a gas supply step, an electrical field generating step and a film-transporting step, in a reaction chamber for carrying out the manufacturing method therein. The electrical field generating step uses a power-feeding electrode and a grounding electrode. The grounding electrode is arranged so that a distance between the surface of a plastic film being transported and the surface of the grounding electrode can change along a transportation direction of the plastic film in the film transporting step, so that an impedance of the grounding electrode can change along the transportation direction of the plastic film, or so that the distance and the impedance can change at the same time. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a production apparatus for producing a gas barrier film, and more specifically, an apparatus capable of producing a gas barrier film having flexibility while ensuring high gas barrier properties, and the apparatus. The present invention relates to a gas barrier film obtained by a production apparatus.

  Conventionally, various image display devices, electronic display element substrates, solar cell substrates, and the like have been described as being important for their ability to transmit gas and water vapor (hereinafter also referred to as “gas barrier properties”). Therefore, the use of a glass plate has been widely performed.

  Certainly, when a glass plate is used for the substrate, various gases and water vapor do not pass through the glass plate, so that those located inside the glass plate are protected from various gases and water vapor from the outside. However, on the other hand, problems in handling such as easy breakage of the glass plate and increase in weight have been pointed out.

  Therefore, a transparent plastic film has been attracting attention as a substrate that is flexible, difficult to break, and lightweight against a relatively heavy glass plate that is easily broken.

  However, since the plastic film permeates gas and water vapor, the plastic film does not have the gas barrier property as described above, and therefore, the plastic film cannot be used as it is without any processing.

  Accordingly, various studies have been made to develop a plastic film having a gas barrier property (hereinafter also referred to as a “gas barrier film”) by applying some processing or treatment to the plastic film. In the early stages of development, development related to laminating metal on the surface of a plastic film has been made, but eventually it becomes an important theme to obtain transparency as well as gas barrier properties, and there is also a demand for improving gas barrier properties. While the film is growing, while maintaining transparency by laminating thin film layers mainly made of oxides, nitrides, oxynitrides, fluorides, etc. of silicon, aluminum, indium, magnesium, etc. on the surface of plastic films Various attempts have been made to obtain higher gas barrier properties.

  In order to simply laminate such a group of materials on the surface of a transparent plastic film, a physical vapor deposition method (hereinafter also referred to as “PVD method”), a chemical vapor deposition method (hereinafter referred to as “CVD method”). Or a coating method (hereinafter also referred to as “sol-gel method”). Among these methods, it can be said that the CVD method is most suitable for producing a gas barrier film. This is because when PVD method is used, certainty at the time of lamination is not sufficient, high vacuum conditions are required, and further, cracks are likely to occur in the laminate, that is, gas barrier properties are impaired from cracks. In the case of the sol-gel method, a coating solution obtained by dissolving a raw material in a solvent is applied onto a plastic film and then dried. This is because it is very difficult to secure a necessary and sufficient gas barrier property by generating a large bubble.

  Thus, it can be said that it is theoretically preferable to use a method called a plasma chemical vapor deposition method (plasma CVD method) for producing a gas barrier film. This is because the plastic film used as the base material of the gas barrier film is vulnerable to high heat treatment, and the high temperature applied to the base material in the plasma CVD method is a temperature that can withstand even a plastic film. When a certain substance is laminated on the surface of the plastic film, it can be said that the plasma CVD method is preferable.

  For example, Patent Document 1 discloses this plasma CVD method as an invention that provides a technique for improving the yield and the film forming speed.

JP 2005-200710 A

  The invention disclosed in Patent Document 1 is a method for quickly and efficiently vapor-depositing by devising a plasma discharge method if necessary, and according to such a method, a gas barrier film can be quickly obtained with high yield. Can be obtained.

  However, with this alone, it is possible to obtain a gas barrier film with good yield and quickly, and there is a request to obtain a gas barrier film that maintains the flexibility as a film while securing the high gas barrier property that is the original problem. It cannot be said to have responded enough.

  That is, the invention described in Patent Document 1 efficiently manufactures a gas barrier film having characteristics equivalent to those of a conventional product. Compared with the properties of a conventional product, which has recently been increasing in demand, However, it has not been able to meet the market demand for improving flexibility and ensuring flexibility as before.

  The present invention has been made in view of such problems, and the object thereof is to improve the gas barrier property as seen in the conventional gas barrier film, which has high gas barrier properties but low flexibility or sufficient flexibility. Compared to the characteristics such as not being possible, a manufacturing method for manufacturing a gas barrier film that can achieve high gas barrier properties and at the same time ensure the same flexibility, a device that can realize the manufacturing method, and the manufacturing method or the manufacturing It is to provide a gas barrier film obtained by the apparatus.

  In order to solve the above-mentioned problems, the manufacturing method according to claim 1 of the present invention is directed to plasma chemistry of a gas barrier film, which is a film having a gas barrier property that does not allow gas such as oxygen and water vapor to permeate a plastic film as a substrate. A manufacturing method for manufacturing by vapor phase growth method (plasma CVD method), wherein the manufacturing method is a vacuum process for making the inside of the chamber at a vacuum state at least in a reaction chamber for executing the manufacturing method; A gas supply step for introducing a source gas for imparting the gas barrier property while using a carrier gas in the reaction chamber; an electric field generation step for applying a high-frequency electric field in the reaction chamber; and the reaction A film transporting step for transporting the plastic film indoors, and the electric field generating step comprises a feeding electrode and a ground electrode. The plastic film is transported in the film transporting step between the feeding electrode and the ground electrode, and the ground electrode is formed of the plastic film in the film transporting step. The distance between the surface of the plastic film being transferred and the surface of the ground electrode is changed along the transfer direction, or the impedance of the ground electrode is changed along the transfer direction of the plastic film, or They are characterized in that they are installed so that the distance and the impedance change simultaneously.

  A manufacturing method according to claim 2 of the present invention is the method for manufacturing a gas barrier film according to claim 1, wherein the carrier gas is a mixture of argon, oxygen, or hydrogen. The source gas is alkoxysilane.

  The manufacturing apparatus according to claim 3 of the present invention is a plasma chemical vapor deposition method (plasma CVD method), which is a gas barrier film that has a gas barrier property that does not allow gas such as oxygen or water vapor to permeate a plastic film as a substrate. And a vacuum means for making the inside of the reaction chamber a vacuum state at least in a reaction chamber for executing the production method, and the gas barrier property in the reaction chamber. A gas supply means for introducing a raw material gas for applying, an electric field generating means for applying a high-frequency electric field in the reaction chamber, and a film conveying means for conveying the plastic film in the reaction chamber. The electric field generating means comprises a feeding electrode and a ground electrode, and the film conveying means includes The plastic film is transported between the feeding electrode and the ground electrode, and the ground electrode is transported along the transport direction of the plastic film in the film transport process. As the distance between the surface and the surface of the ground electrode changes, or so that the impedance of the ground electrode changes along the transport direction of the plastic film, or so that the distance and the impedance change simultaneously. It is characterized in that they are installed.

  A manufacturing method according to claim 4 of the present invention is the gas barrier film manufacturing apparatus according to claim 3, wherein the carrier gas is a mixture of argon, oxygen, or hydrogen, or a plurality thereof. The source gas is alkoxysilane.

  A gas barrier film according to a fifth aspect of the present invention is obtained by any one of the method for producing a gas barrier film according to the first or second aspect or the apparatus for producing a gas barrier film according to the third or fourth aspect. It is characterized by being made.

  As described above, if the method for producing a gas barrier film according to the invention of the present application, in short, a high-frequency electric field is applied to collide electrons with the raw material gas to make the raw material gas into plasma, which is used as a base material for the transparent plastic film. When forming a thin film by stacking on the surface, it is installed on both sides where such transparent plastic is conveyed, against the plane of the transparent plastic film where the supply electrode and ground electrode for applying a high frequency electric field are conveyed Since the gas barrier film obtained by this manufacturing method is a conventional case and has a high gas barrier property, since the density is high, that is, hard and brittle, the obtained gas barrier film is Although it has a high gas barrier property, it lacks flexibility, while the opposite, that is, to ensure flexibility Although only a thin film with a low density is laminated, flexibility is provided, but the gas barrier property is not so high. On the other hand, while maintaining high gas barrier property, the flexibility of the transparent plastic film is also to some extent It can be secured. In the present invention, since the plus electrode is provided at one end of the ground electrode, the inclination of the electric field can be freely controlled by the influence of the plus electrode, so that the degree of design freedom is further increased. It can be said that it becomes higher. In addition, silicon oxynitride (SiOxCy) is used as a gas barrier layer for imparting gas barrier properties, and in order to form such a gas barrier layer, a low-toxic alkoxysilane is used as a starting material, and at the same time, either argon, oxygen, or hydrogen or If a mixed gas is used at the same time, it is possible to avoid the generation of a large amount of toxic cyanide.

  Embodiments of the present invention will be described below. The embodiment shown here is merely an example, and is not necessarily limited to this embodiment.

(Embodiment 1)
A manufacturing method for manufacturing a gas barrier film, which is a film having a gas barrier property that does not allow gas such as oxygen and water vapor, to permeate a plastic film as a base material according to the present invention by plasma chemical vapor deposition (plasma CVD method) (Hereinafter, also simply referred to as “manufacturing method”), a manufacturing apparatus for carrying out such a manufacturing method will be described as a first embodiment with reference to the drawings.

  First, the entire manufacturing method according to the present embodiment will be described. This manufacturing method includes at least a vacuum process for making the inside of the reaction chamber in a vacuum state in the reaction chamber in which the manufacturing method is executed, and imparts gas barrier properties to the inside of the reaction chamber A method comprising: a gas supply process for introducing a raw material gas for performing a process; an electric field generation process for applying a high-frequency electric field in the reaction chamber; and a film transport process for transporting the plastic film in the reaction chamber It is. At the same time, the electric field generating step uses a feeding electrode (cathode), a ground electrode (anode), and a plus electrode.

  In the following, description will be made with reference to FIGS. 1 and 2 showing the concept of the apparatus for further carrying out the present embodiment.

  First, the reaction chamber 12 is necessary to carry out the manufacturing method according to the present embodiment, which is also referred to as a vacuum chamber. In the plasma CVD method to which the manufacturing method according to the present embodiment belongs in the first place, Of course, the reaction chamber may be a general reaction chamber required for a conventionally known plasma CVD method. For the reason described later, the inner wall surface 12 of the reaction chamber in the present manufacturing method is, for example, insulated. It is preferable that the body is covered with an insulation treatment such as being entirely covered. In the following description, the reaction chamber 12 is assumed to be insulated. In addition, all the steps described further below are basically performed in the reaction chamber 12, or even if the steps prepared outside the reaction chamber 12 are actually performed in the reaction chamber 12. I refuse to do that.

  First, the vacuum process in the present embodiment will be described. This is a process for making the inside of the reaction chamber 12 vacuum, and the atmosphere around the reaction is vacuumed as much as possible in order to improve the reactivity when performing the plasma CVD method. It can be said that it is a necessary process because it is preferable to set the state. Although the reaction chamber is in a substantially vacuum state by this vacuum process, an exhaust pump 9 is provided in the present embodiment to perform this process. The exhaust pump 9 may be a conventionally known one, and further detailed description thereof will be omitted here.

  Next, a gas supply process for introducing a raw material gas for imparting a gas barrier property to the inside of the reaction chamber 12, which is also realized by an apparatus used for performing a conventionally known plasma CVD method. In order to realize such a process, for example, as shown in FIG. 1, the carrier gas passes through the mass flow controller 5 from the carrier gas cylinder 6 and the monomer raw material 8 passes through the liquid mass flow controller 7 at the same time. Then, the gas is discharged into the reaction chamber 12 through the gas pipe 10.

  That is, the monomer raw material 8 is released into the reaction chamber 12 by the carrier gas in the gas supply process, but this monomer raw material 8 becomes a raw material for imparting gas barrier properties to the plastic film as the base material. .

  As the monomer raw material 8, conventionally known materials may be used. For example, silicon oxide carbide or silicon oxide is widely used. In this embodiment, alkoxysilane is used. The carrier gas serves to carry the monomer raw material 8 into the reaction chamber 12 as described above. This carrier gas may also be a conventionally known one, for example, argon, oxygen, nitrogen or the like alone or Any of these may be used as a mixture, and oxygen is used in this embodiment. When the plasma treatment is performed using alkoxysilane and oxygen in this manner, SiOxCy (silicon oxide carbide) is deposited on the base plastic film to form a SiOxCy layer that exhibits gas barrier properties. In this regard, the conventional manufacturing method for forming a SiCxNy (silicon carbonitride) film may generate toxic cyan, so it is suitable for mass production even if a highly functional gas barrier film is obtained. However, it can be said that such a risk can be eliminated by the manufacturing method according to the present embodiment in which the above-described SiOxCy film is deposited and used as a layer. Note that the thickness of the gas barrier film in the present embodiment is preferably 100 nm or more and 3000 nm or less. However, if the thickness is less than 100 nm, the layer cannot exhibit sufficient gas barrier properties even if SiOxCy is laminated. This is because if the thickness exceeds 3000 nm, the thickness of the entire gas barrier film obtained is unnecessarily thick.

  Further, the plastic film as the base material in the whole process is transported by the film transporting process, and an apparatus for realizing this may be a conventionally known apparatus, that is, the base plastic film is unloaded from the unwinding 3, Various processes are performed on the way, and it is wound on the winding 4.

  The manufacturing method according to the present embodiment basically undergoes the above steps, that is, in the reaction chamber 12 in which the entire process is performed and the chamber is subjected to insulation treatment, the vacuum process is first performed. As a result, the inside of the reaction chamber 12 is brought into a substantially vacuum state, and in the substantially vacuum state, the plastic film as the base material is transported in the reaction chamber 12 by the film transporting process, and the base material plastic film is transported in the process of transporting the base material plastic film. The surface of the substrate is exposed to an electric field generated by an electric field generation process comprising a cathode and an anode, and at the same time, a monomer raw material for imparting a gas barrier property is released into a reaction chamber in a substantially vacuum state by the gas supply process. Is turned into plasma by the electric field generation process, and the plasmaized monomer becomes the base plastic film Becomes a layer attached to a surface, such a layer functions as a gas barrier layer, and finally the gas barrier film is obtained, is a process called. In addition, a conventionally known device group is installed in order to enable this process in the present embodiment.

  The manufacturing method according to the present embodiment is as described above. However, in this embodiment, the method of generating an electric field in the electric field generating step is different from the manufacturing method by the conventional plasma CVD method. I will explain.

  In the conventional electric field generation process, it was important that the surface of the anode was parallel to the surface of the base plastic film being transported in the film transport process. This is because the electric field applied to the base plastic film surface is always uniform. This is because it is necessary that the plasma monomer is laminated on the base plastic film because the electric field is uniform. In other words, by uniformly laminating the monomers, the density of the laminating is the same or nearly the same regardless of which part is taken out. Therefore, by uniformly laminating the monomers for imparting gas barrier properties, the gas barrier properties are uniform. This is because the properties of the obtained gas barrier film are uniform over the entire film. Or, in the conventional process, it can be said that the condition that the impedance of one or both of the cathode and the anode is the same in any part may be essential. This is because by making the impedance uniform, the generated electric field is the same and uniform in any part as described above.

  However, in this embodiment, as shown in FIG. 1, the surface of the anode 2 is not parallel to the surface of the base plastic film being transported in the film transporting process, and the distance between them varies depending on the transport direction of the base plastic film. In addition, an anode 2 is installed. And the positive electrode 13 is installed in the direction orthogonal to the conveyance direction of a base-material plastic film at the end of the anode 2.

  For example, in the state shown in FIG. 1, the anode 2 rises to the right along the conveyance direction of the base plastic film (from left to right in the figure), and the bias power source 14 is at the left end of the anode 2. A connected positive electrode 13 is provided. That is, as the base plastic film is conveyed, the distance between the base plastic film surface and the anode 2 surface becomes narrower. As the distance is narrowed in this way, the electron density generated between the anode 2 and the cathode 1 connected to the power source 11 is inclined, and the presence of the plus electrode 13 makes the electron more clearly defined. The density can be tilted.

  In other words, since the plus electrode 13 is installed in this way, the inclination of the electron density described above can be freely changed by setting the location of the plus electrode 13 and the strength of the electrode. This makes it easy to set various types of gas barrier properties.

  And when observing the entire gas barrier film according to the present embodiment obtained by passing the inclined electron density through the base plastic film in this way, the flexibility of the base plastic film is not so much impaired, On the other hand, the gas barrier property of the entire gas barrier film is sufficiently high, that is, when viewed as a whole, a gas barrier film that secures a high gas barrier property as well as flexibility is obtained.

  In the manufacturing method according to the present embodiment, as described above, it is important to gradually incline the electron density with respect to the surface of the base plastic film being transported, but the cathode 1 transports the film as shown in FIG. A configuration that can also be used as a device is also conceivable. That is, it can be said that if the roller for transporting the base plastic film acts as the cathode 1, the entire apparatus can be simplified, which is preferable.

  Furthermore, in any case, in order to reliably apply an electric field to the surface of the substrate plastic film being conveyed, it is necessary to apply an electric field only to a necessary part, but this is not necessary. This means that an electric field must not be applied to the place, and for this purpose, the entire reaction chamber 12 must be insulated. By applying insulation treatment, an electric field is generated only at the necessary location. As a result, an electric field is applied only to the surface of the substrate plastic film being transported, and the plasma monomer adheres only to the surface of the substrate plastic film. Thus, a gas barrier layer is formed.

  In addition, the gas barrier layer in the present embodiment is the SiOxCy layer as described above, but the film deposited at the position where the distance between the electrodes is farthest from the Si density of the film deposited at the position where the electrode distance is closest. The gas barrier layer is preferably laminated so that the Si density is at least 0.6 times or less. This is because the inclination with such a difference can achieve both sufficient flexibility and high gas burrability.

  The above explanation relates to the case where the anode installation method is physically changed. However, although the anode is installed in parallel with the transport direction of the base plastic film as usual, the impedance at the anode is the same as that of the base plastic film. It is conceivable to set it to be inclined along the transport direction. In this case, the same effect can be obtained because the generated electric field is inclined as described above, and the physical installation method of the anode is also inclined. It is also possible to further incline the impedance, but the results obtained are the same in any case, and further details are omitted here.

  Thus, if it is the manufacturing method concerning this Embodiment, or the manufacturing apparatus which implement | achieves this manufacturing method, the gas barrier film obtained can have a high gas barrier property and also a flexibility. The gas barrier film obtained by such a production method or production apparatus can have both flexibility and high bus barrier properties.

It is the figure which showed the outline of the manufacturing apparatus concerning this Embodiment It is the figure which showed the outline of another manufacturing apparatus concerning this Embodiment

Explanation of symbols

1 Cathode (power supply electrode)
2 Anode (ground electrode)
3 Unwinding 4 Rewinding 5 Mass flow controller 6 Carrier gas cylinder 7 Liquid mass flow controller 8 Monomer raw material 9 Exhaust pump 10 Gas pipe 11 Power supply 12 Vacuum reaction chamber 13 Positive electrode 14 Bias electrode

Claims (5)

A gas barrier film, which is a film having a gas barrier property that does not allow gas such as oxygen and water vapor to permeate a plastic film as a base material, is produced by a plasma chemical vapor deposition method (plasma CVD method),
The production method is at least
In the reaction chamber for carrying out the manufacturing method, a vacuum process for making the inside a vacuum state
A gas supply step for introducing a source gas for imparting the gas barrier property while using a carrier gas in the reaction chamber;
An electric field generating step for applying a high frequency electric field in the reaction chamber;
A film transporting process for transporting the plastic film in the reaction chamber;
With
The electric field generating step is performed using a feeding electrode, a ground electrode, and a plus electrode,
Transport of the plastic film in the film transport process is performed between the power supply electrode and the ground electrode,
The ground electrode is arranged such that a distance between the surface of the plastic film being conveyed and the surface of the ground electrode is changed along the conveyance direction of the plastic film in the film conveyance process, or the impedance of the ground electrode is the plastic At the same time that they are installed so as to change along the film transport direction or so that the distance and the impedance change at the same time, the plus electrode is in the direction perpendicular to the plastic film transport direction and the grounding Provided at either end of the electrode,
A method for producing a gas barrier film, characterized in that It is a manufacturing method of the gas barrier film according to claim 1,
The carrier gas is a mixture of argon, oxygen, or hydrogen, or the source gas is an alkoxysilane;
A method for producing a gas barrier film, characterized in that A manufacturing apparatus for manufacturing a gas barrier film, which is a film having a gas barrier property that does not allow gas such as oxygen and water vapor to permeate a plastic film as a base material, by a plasma chemical vapor deposition method (plasma CVD method),
The manufacturing apparatus is at least
In the reaction chamber for carrying out the manufacturing method, vacuum means for making the inside a vacuum state;
A gas supply means for introducing a raw material gas for imparting the gas barrier property into the reaction chamber;
An electric field generating means for applying a high frequency electric field in the reaction chamber;
Film transport means for transporting the plastic film in the reaction chamber;
With
The electric field generating means comprises a power supply electrode, a ground electrode, and a positive electrode;
Transport of the plastic film in the film transport means is performed between the power supply electrode and the ground electrode,
The ground electrode is arranged such that a distance between the surface of the plastic film being conveyed and the surface of the ground electrode is changed along the conveyance direction of the plastic film in the film conveyance process, or the impedance of the ground electrode is the plastic At the same time that they are installed so as to change along the film transport direction or so that the distance and the impedance change at the same time, the plus electrode is in the direction perpendicular to the plastic film transport direction and the grounding Provided at either end of the electrode,
An apparatus for producing a gas barrier film. An apparatus for producing a gas barrier film according to claim 3,
The carrier gas is a mixture of argon, oxygen, or hydrogen, or the source gas is an alkoxysilane;
A method for producing a gas barrier film, characterized in that A gas barrier film manufacturing method according to claim 1 or claim 2 or a gas barrier film manufacturing apparatus according to claim 3 or claim 4,
A gas barrier film characterized by

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