JP5092624B2 - Method and apparatus for producing gas barrier film - Google Patents

Description

  The present invention relates to a method and apparatus for producing a gas barrier film on a long film by an atomic layer deposition method, and a gas barrier film obtained thereby.

  In recent years, attempts have been widely made to produce, for example, an organic EL display or a semiconductor device on a flexible substrate. In this case, the problem is the low gas barrier property of the base material made of a polymer material. Since many of the light emitting materials constituting the organic EL element and the semiconductor materials constituting the semiconductor element are deteriorated by water or oxygen, improvement of gas barrier properties is important. Based on this background, gas barrier materials are vacuum-deposited or wet coated on a polymer substrate to improve the gas barrier properties of the substrate, but it is still not suitable for organic EL device applications. Satisfactory high gas barrier properties have not been realized. The cause is not sufficiently clarified, but it is considered that the main cause is unevenness of the base material or a defect due to foreign matter.

Under such circumstances, Patent Document 1 proposes forming a gas barrier layer in a color organic EL display by an atomic layer growth method having a dense and few pinholes. Patent Document 2 also forms a dense thin film having a good barrier property regardless of irregularities and defects on the substrate surface by forming a barrier layer by an atomic layer deposition method (ALD method) in an organic EL element. It has been proposed that it can be done.
JP 2006-253106 A JP2007-90803

  The gas barrier film produced by the method proposed in the above Patent Documents 1 and 2 is in line with the unevenness and defects of the base material, even when there are unevenness of the base material and defects due to foreign matters that are difficult to avoid. Since it is formed as a uniform monoatomic layer stack, it is considered that a dense and homogeneous film is obtained, and as a result, a gas barrier film having a small number of layers and having excellent barrier performance can be obtained.

  However, the film formation method by the atomic layer deposition method generally advances the film formation by one atomic layer by repeatedly introducing and evacuating the source gas in the film formation chamber, so that a film having a predetermined thickness is obtained. Has a problem that it takes a long time and the cost is significantly increased. In practice, it takes a lot of time to introduce and exhaust gas.

  The present invention has been made to solve the above-described problems, and its purpose is to produce a gas barrier film capable of efficiently and inexpensively producing a gas barrier film having excellent gas barrier properties by an atomic layer deposition method. It is to provide a method and a manufacturing apparatus. Another object of the present invention is to provide a gas barrier film having an excellent gas barrier property obtained by the method for producing a gas barrier film.

  The method for producing a gas barrier film of the present invention for solving the above-described problems is a gas barrier comprising a monoatomic layer laminate by an atomic layer deposition method on a base film while continuously moving the long base film. A method for producing a film, comprising: a first source gas supply step for supplying a first source gas for forming a monoatomic layer in a moving direction of the base film; and a second source gas for forming a monoatomic layer. Provided between the first source gas supply step and the second source gas supply step in order to prevent the supply of the second source gas supply step and the mixing of the first source gas and the second source gas. And an atomic layer deposition process in which a large number of at least three kinds of steps having a buffering step are arranged in succession.

  According to the present invention, an atomic layer deposition process in which a large number of at least three steps having a first source gas supply step, a second source gas supply step, and a buffering step are successively arranged in the moving direction of the base film. Therefore, it is possible to produce a gas barrier film composed of a monoatomic layer laminate by an atomic layer deposition method on a base film by continuously moving a long base film in the atomic layer deposition step. it can. According to the present invention, since a number of dedicated processing steps are continuously arranged in the moving direction of the base film, not a batch type in which film formation is performed in a single chamber as in the prior art, gas introduction Time and exhaust time can be saved, and productivity can be greatly improved. As a result, productivity can be greatly improved, and the deposition cost of the gas barrier film can be significantly reduced.

  A preferred embodiment of the method for producing a gas barrier film of the present invention includes a processing time T1 in the first source gas supply step, a processing time T2 in the second source gas supply step, and a processing time T3 in the buffer step. Is configured such that T3> T1 ≧ T2.

  According to this invention, since the processing time T3 of the buffer step provided between the first source gas supply step and the second source gas supply step is the longest, the first source gas is mixed into the second source gas supply step. It is possible to prevent the second source gas from being mixed into the first source gas supply step. The processing time T1 in the first source gas supply step is equal to or longer than the processing time T2 in the second source gas supply step when the first source gas usually has a higher molecular weight than the second source gas. This is because the movement speed of the first source gas having a large molecular weight is slow.

  In a preferred aspect of the method for producing a gas barrier film of the present invention, the first source gas supply step is a step of supplying any compound gas selected from Al compound gas, Zr compound gas and Hf compound gas, The two source gas supply steps are configured to supply any gas selected from a water vapor-containing gas, an oxygen-containing gas, and an ozone-containing gas.

According to this invention, the first source gas supply step is a step of supplying any one of the above compound gases, and the second source gas supply step is a step of supplying any of the above gases. In the supplying step, the compound gas is adsorbed on the base film, and in the second source gas supplying step after the next buffering step, the adsorbed compound gas and the second source gas react to form a monoatomic layer. After the first source gas supply step after the next buffer step, the formation of these monoatomic layers is repeated, and a monoatomic layer stack can be formed. Since these source gases can form a monoatomic layer stack made of any of Al ₂ O ₃ , ZrO ₂ , and HfO ₂ that can be formed at a low temperature, a gas barrier film can be formed under a low temperature condition. .

A preferred embodiment of the method for producing a gas barrier film of the present invention is configured such that the monomolecular layered product is any one selected from Al ₂ O ₃ , ZrO ₂ , and HfO ₂ .

  According to this invention, since the monoatomic layered product made of the above inorganic compound capable of forming a film at a low temperature is formed on the base film without defects, a gas barrier film having excellent gas barrier properties can be obtained.

  An apparatus for producing a gas barrier film according to the present invention for solving the above-described problems is a gas barrier comprising a monoatomic layer laminate by an atomic layer deposition method on a base film while continuously moving the long base film. An apparatus for producing a film, comprising: a supply device that supplies the base film; a storage device that stores the base film after the monoatomic layer stack is formed; and the supply device and the storage device. A monoatomic layer deposition apparatus for depositing a monoatomic layer provided therebetween, and the monoatomic layer deposition apparatus transports the substrate film at a constant speed in a state where the base film is in contact with the surface; A first source gas supply chamber for supplying a first source gas for forming a monoatomic layer provided on the outer periphery of the drum; and a second source for forming a monoatomic layer provided on the outer periphery of the drum. Second source gas supply for supplying gas A source gas in the first source gas supply chamber and the second source gas supply chamber provided between the first source gas supply chamber and the second source gas supply chamber on the outer periphery of the chamber and the drum A plurality of processing chambers having at least three kinds of processing chambers having a buffer chamber for preventing the raw material gas from being mixed are arranged in succession.

  According to this invention, since it has at least the supply device, the storage device, and the monoatomic layer deposition device, the gas barrier formed of the monoatomic layer stack by the atomic layer deposition method on the base film supplied from the supply device A film can be made. In particular, the atomic layer deposition apparatus is not a batch type in which film formation is performed in a single chamber as in the prior art, but a large number of dedicated processing chambers are continuously arranged on the drum surface for transporting the substrate film. Gas introduction time and exhaust time in the processing chamber can be saved, and productivity can be greatly improved. As a result, the film formation cost of the obtained gas barrier film can be significantly reduced.

  A preferable aspect of the gas barrier film manufacturing apparatus of the present invention is that the processing length L1 of the first source gas supply chamber, the processing length L2 of the second source gas supply chamber, and the processing length L3 of the buffer chamber The relationship is such that L3> L1 ≧ L2.

  According to this invention, since the processing length L3 of the buffer chamber provided between the first source gas supply chamber and the second source gas supply chamber is the longest, the first source gas in the first source gas supply chamber Can be prevented from being mixed into the second raw material gas supply chamber or the second raw material gas in the second raw material supply chamber can be prevented from being mixed into the first raw material gas supply chamber. The process length L1 of the first source gas supply chamber is equal to or longer than the process length L2 of the second source gas supply chamber when the molecular weight of the first source gas is usually larger than that of the second source gas. This is because the movement speed of the first source gas having a large molecular weight is slow.

  In a preferred aspect of the gas barrier film manufacturing apparatus of the present invention, a common gas supply pipe is connected to each of the first and second source gas supply chambers provided on the outer periphery of the drum, At least the entire atomic layer deposition apparatus other than the first and second source gas supply chambers is held in a reduced pressure exhaust atmosphere.

  According to the present invention, since the common gas supply pipes are connected to the first and second source gas supply chambers, for example, the first and second source gases are supplied from the respective source gas supply apparatuses through one system of pipes. It can be sent to the second source gas supply chamber, and the device configuration can be simplified. In addition, since at least the entire atomic layer deposition apparatus other than the first and second source gas supply chambers is held in a reduced pressure exhaust atmosphere, there is no need to provide exhaust pipes for each of the buffer chambers. The inflowing first and second source gases can be discharged out of the atomic layer deposition apparatus held in a reduced pressure exhaust atmosphere, and the apparatus configuration can be simplified.

  In a preferred aspect of the gas barrier film manufacturing apparatus of the present invention, the first source gas supply chamber, the second source gas supply chamber, and the drum are configured to be heated by heating means.

  According to the present invention, the first source gas supply chamber, the second source gas supply chamber, and the drum can be heated, so that the reaction temperature necessary for forming the monoatomic layer can be arbitrarily given.

  A preferred embodiment of the gas barrier film production apparatus of the present invention is an apparatus in which the supply device supplies a roll-shaped base film, and the storage device has the base film after the monoatomic layer stack is formed. It is a winding apparatus, Comprising: It comprises so that supply operation | movement of the base film by this supply apparatus and winding operation | movement of the base film by this accommodating apparatus may be replaced | exchanged for every fixed time.

  According to this invention, since the supply operation of the base film by the supply device and the winding operation of the base film by the storage device can be switched at regular intervals, for example, the base film can be rolled, rolled, rolled Can be reciprocated across the atomic layer deposition apparatus. By such reciprocating means, a gas barrier film having a predetermined thickness can be formed by repeatedly forming a monoatomic layer.

  The gas barrier film of the present invention for solving the above-mentioned problems is characterized in that a gas barrier film is formed on a long base film by the method for producing a gas barrier film according to the present invention.

  According to the present invention, even if there are unevenness of the base film and defects due to foreign matters that are difficult to avoid, it consists of a uniform and dense monoatomic layer laminate along the unevenness and defects of the base film. A gas barrier film is obtained by obtaining a gas barrier film at a lower cost than conventional ones.

A preferred aspect of the gas barrier film of the present invention is configured such that the gas barrier film is any one selected from Al ₂ O ₃ , ZrO ₂ , and HfO ₂ .

  According to this invention, since the gas barrier film made of the above inorganic compound capable of low-temperature film formation is formed on the base film without defects, the gas barrier film is excellent in gas barrier properties.

  According to the method for producing a gas barrier film of the present invention, a long base film is continuously moved in an atomic layer deposition step, thereby forming a monoatomic layer laminate by an atomic layer deposition method on the base film. Since a gas barrier film can be produced, productivity can be significantly improved. In addition, since gas introduction time and exhaust time can be saved, productivity can be greatly improved compared to gas barrier films obtained by conventional atomic layer deposition methods, and the gas barrier film deposition costs are significantly reduced. Can be made.

  According to the gas barrier film production apparatus of the present invention, a gas barrier film made of a monoatomic layer laminate by an atomic layer deposition method can be produced on a base film supplied from a supply apparatus, so that productivity is greatly improved. Can be improved. In particular, the atomic layer deposition apparatus according to the present invention is not a batch type in which film formation is performed in a single chamber as in the prior art, but a large number of dedicated processing chambers are continuously arranged on the drum surface for transporting the substrate film. Therefore, the gas introduction time and the exhaust time in each processing chamber can be saved, and as a result, the film formation cost of the obtained gas barrier film can be significantly reduced.

  According to the gas barrier film of the present invention, uniform and dense monoatomic layer lamination along the unevenness and defects of the base film, even when the unevenness of the base film and defects due to foreign matters exist that are difficult to avoid A gas barrier film made of a body can be provided as a gas barrier film obtained at a lower cost than before.

  Next, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and may be arbitrarily modified within the scope of the present invention. can do. First, a gas barrier film manufacturing apparatus will be described, and then a gas barrier film manufacturing method and a gas barrier film obtained by the method will be described.

[Gas barrier film production equipment]
FIG. 1 is a schematic configuration diagram illustrating an example of a gas barrier film manufacturing apparatus according to the present invention, and FIG. 2 is a cross-sectional configuration diagram illustrating an example of a gas barrier film obtained by the manufacturing apparatus according to the present invention. As shown in FIG. 1, the gas barrier film production apparatus 10 of the present invention has a monoatomic layer formed by atomic layer deposition on the base film 2 while continuously moving the long base film 2. It is an apparatus for producing a gas barrier film 1 composed of a 1 ′ laminate (also referred to as a monoatomic layer laminate). The apparatus 50 includes at least a supply device 51, a storage device 52, and a monoatomic layer deposition device 53. Hereinafter, each component will be described.

(Supply device)
The supply device 51 is a device for supplying a long base film 2 and has, for example, a clamp member (not shown) that holds the roll-shaped film 11 wound on the core material 12 rotatably from both sides. ing. The supply device 51 includes a drive motor (not shown) that can be controlled so that the base film 2 can be fed out at a constant speed. Sending control by the drive motor can be performed, for example, by receiving a rotation signal of a rotary encoder (not shown) provided on one of the guide rollers 54. Further, in order to stably supply the base film 2 sent out from the supply device 51 to the monoatomic layer deposition device 53 under a constant tension, for example, between the supply device 51 and the monoatomic layer deposition device 53 A damper 54 for tension adjustment may be provided in the area denoted by reference numeral 56.

(Container)
The storage device 52 is a device for storing the gas barrier film 1 produced on the base film 2 (also referred to as a film 2 ′, see FIG. 2), and usually winds the film 2 ′ on the core material 14. Although a winding apparatus can be illustrated, the folding apparatus (not shown) which can fold film 2 'for every fixed length may be sufficient. In addition, when the accommodating apparatus 52 is a winding apparatus, the apparatus etc. which can be wound up in the state which loaded the fixed torque can be illustrated.

(Monoatomic layer deposition equipment)
The monoatomic layer deposition apparatus 53 is an apparatus for depositing the monoatomic layer 1 ′ (see FIG. 2) by an atomic layer deposition method, provided between the supply apparatus 51 and the accommodation apparatus 52. In the monoatomic layer deposition apparatus 53, a large number of at least three kinds of processing chambers having a first source gas supply chamber 62, a second source gas supply chamber 63, and a buffer chamber 64 are continuously arranged on a drum 61. It is made.

  Here, the atomic layer deposition method will be described. The atomic layer deposition method is also called an atomic layer epitaxy (ALE) method or an atomic layer deposition (ALD) method. For example, in the case of forming the gas barrier film 1 composed of the monoatomic layer 1 ′ with the two source gases by the atomic layer deposition method, first, the first source gas is introduced onto the base film 2 and then the base material is formed by chemical adsorption. A molecular layer composed of the first source gas is formed on the material film 2, and then the second source gas is guided onto the base film 2 in an atmosphere in which the first source gas does not exist, A monoatomic layer 1 ′ is formed by a chemical reaction occurring between the first and second layers, and then the first source gas and the second source gas are again formed on the monoatomic layer 1 ′ in an atmosphere in which the second source gas does not exist. The gas barrier film 1 made of a monoatomic layer stack is formed by sequentially laminating the monoatomic layers 1 ′. This atomic layer deposition method is characterized in that the reaction stops at a monoatomic layer, so if the source gas reaches, the formation of a molecular layer by adsorption of the source gas and the reaction of the molecular layer with another source gas By repeating with the formation of the monoatomic layer by, for example, a uniform monoatomic layer can be formed along the irregularities and protrusions even on a base film on which irregularities and protrusions inevitably exist.

  The drum 61 rotates so as to convey the base film 2 at a constant speed while the base film 2 is in contact with the surface thereof. Usually, a cylindrical drum having a width equal to or larger than the width of the base film 2 is used. The diameter of the drum 61 is not particularly limited, and the structure is designed according to the length and number of processing chambers (62 to 64) provided on the outer periphery of the drum 61, the conveyance speed of the base film 2, and the like.

  It is preferable that a heating means for heating the base film 2 is added to the drum 61. Various heating means for the drum 61 can be mentioned, for example, a path through which the heat medium discharged from the chiller (cooler) is passed inside the drum, and means for transferring heat to the drum surface, A means for heating the drum surface by providing an IR lamp on the upper part of the film forming drum (the part not filmed) and a plasma heating device on the upper part of the film forming drum (the part not filmed) for heating the drum surface. Examples thereof include means for winding the heater around the drum 61, and the like. If the temperature of the drum surface is controlled by such heating means, for example, the base film 2 can be activated so that the source gas is easily adsorbed on the base film 2. In addition, as such temperature, it is preferable that it is as high as possible in the range which does not exceed the glass transition temperature of the base film 2, or the decomposition start temperature of the base film 2. However, if the temperature is too high, the adsorbed molecules of the source gas are desorbed from the base film 2 or the base film 2 is damaged. Therefore, the base film 2 is set at a temperature at which such a phenomenon does not occur. It is necessary to adjust appropriately according to the type of the gas and the type of the source gas. As an example of the temperature of the base film 2, it is the range of 30 to 300 degreeC, for example, Preferably it is the range of 50 to 250 degreeC. On the other hand, if the temperature is too low, a reaction may not occur and a monoatomic layer may not be formed, or raw materials may aggregate on the substrate surface.

  The first source gas supply chamber 62 is a processing chamber that is provided on the outer periphery in the rotation direction of the drum 61 and supplies the first source gas for forming the monoatomic layer onto the base film 2. The second source gas supply chamber 63 is a processing chamber that is provided on the outer periphery in the rotation direction of the drum 61 and supplies the second source gas for forming the monoatomic layer onto the base film 2. The buffer chamber 64 is a processing chamber provided on the outer periphery in the rotation direction of the drum 61 and provided between the first source gas supply chamber 62 and the second source gas supply chamber 63. It is provided to prevent the first source gas in the source gas supply chamber 62 and the second source gas in the second source gas supply chamber 63 from entering each supply chamber.

  In the example shown in FIG. 1, these processing chambers are arranged from the supply device 51 side from the first source gas supply chamber 62, the buffer chamber 64, the second source gas supply chamber 63, the buffer chamber 64, and the first source gas supply chamber. 62, buffer chamber 64, second source gas supply chamber 63,..., Second source gas supply chamber 63 are arranged in succession in this order.

  In each of the first source gas supply chamber 62, the second source gas supply chamber 63, and the buffer chamber 64, a gap 70 is provided on the drum 61 side so that the base film 2 can enter each processing chamber. It has been. The size of the gap 70 is not particularly limited as long as the base film 2 conveyed in contact with the surface of the drum 61 is not in contact with each processing chamber. , 64, it can be set to about 1 mm to 10 mm.

In such a monoatomic layer deposition apparatus 53, for example, when Al ₂ O ₃ is produced as the gas barrier film 2, Al (CH ₃ ) ₃ gas is supplied as the first source gas to the first source gas supply chamber 62, and the second The source gas supply chamber 63 is supplied with H ₂ O gas as the second source gas. Then, when the base film 2 is transported on the drum 61 of the monoatomic layer deposition apparatus 53, in the first source gas supply chamber 62, the OH groups present on the base film 2 and the supplied Al (CH ₃ ) ₃ gas is chemisorbed to become O—Al (CH ₃ ) ₃ , and after passing through the buffer chamber 64, the O—Al (CH ₃ ) ₃ and H ₂ O gas are passed through the second source gas supply chamber 63. Chemically react with each other to form O-Al-O to form a monoatomic layer 1 '. After that, by repeating such adsorption / reaction process, the gas barrier film 2 composed of a laminate of the monoatomic layer 1 ′ is formed.

  In the above example, the monoatomic layer stack is formed by using two kinds of source gases. For example, when forming the monoatomic layer stack by using three or more kinds of source gases, the third source gas is used. A supply chamber (not shown) or the like is provided on the drum 61 in such a manner that the buffer chambers 64 are arranged in the front and rear, and a monoatomic layer stack can be formed by repeating similar chemical adsorption and chemical reaction.

  In this monoatomic layer deposition apparatus 53, the processing length of the first source gas supply chamber 62 is L1, the processing length of the second source gas supply chamber 63 is L2, and the processing length of the buffer chamber 64 is L3. When the supply pressure of the raw material gas to each processing chamber is the same pressure for both the first raw material gas and the second raw material gas, it is preferable that the relationship between the processing lengths is L3> L1 ≧ L2.

First, the relationship between the processing length L1 of the first source gas supply chamber 62 and the processing length L2 of the second source gas supply chamber 63 will be described. For example, when producing Al ₂ O ₃ as described above as the gas barrier film 2, the first source gas supplied to the first source gas supply chamber 62 is Al (CH ₃ ) ₃ gas, and the second source gas supply chamber 63. Since the second source gas supplied to is H ₂ O gas, Al (CH ₃ ) ₃ gas has a larger molecular weight and a slower moving speed than H ₂ O gas. Usually, since the moving speed of the base film 2 is constant, the processing length L1 of the first source gas supply chamber 62 provided on the drum 61 is equal to or longer than the processing length L2 of the second source gas supply chamber 63 (L1). ≧ L2), preferably longer than the processing length L2 (L1> L2).

  When the supply pressure P1 of the first source gas is different from the supply pressure P2 of the second source gas, the relationship between the processing lengths L1 and L2 when taking the pressure into consideration is [P1 × L1] ≧ [P2 × L2 ], Preferably [P1 × L1]> [P2 × L2]. In addition, the pressure of each raw material gas is about 10 Pa-1000 Pa normally.

  Next, a case where the processing length L3 of the buffer chamber 64 is also considered will be described. In the example of FIG. 1, at least the monoatomic layer deposition apparatus 53 is in a chamber 71 that can be adjusted to a reduced-pressure atmosphere, and the reduced-pressure atmosphere is set in the chamber 71 by the reduced-pressure apparatus 72. Further, since the buffer chamber 64 has an opening 69 on the opposite side of the drum 61, the buffer chamber 64 has a reduced pressure atmosphere similar to that in the chamber 71. Under such an atmosphere, when the base film 2 drawn out from the supply device 51 enters the first source gas supply chamber 62, the first source gas supply chamber 62 is filled with the first source gas. The adsorption reaction of one source gas on the base film 2 is completed immediately. Therefore, the processing length L1 of the first source gas supply chamber 62 may be short. Similarly, when the base material film 2 chemically adsorbed with the first source gas enters the second source gas supply chamber 63, the second source gas supply chamber 63 is filled with the second source gas. The chemical reaction of the source gas on the base film 2 is also completed immediately. Therefore, the processing length L2 of the second source gas supply chamber 63 may be short.

  On the other hand, the buffer chamber 64 needs to have a longer processing length L3 so that the source gases from the two adjacent supply chambers 62 and 63 do not enter and react with the other source gas supply chambers. . Usually, since the chemical adsorption and chemical reaction of the raw material gas are completed instantaneously, the processing length L3 of the buffer chamber 63 is longer than the processing lengths L1 and L2 of the respective raw material gas supply chambers. > L1 ≧ L2, preferably L3> L1> L2. When the two source gases are mixed, particles are generated, and the particles may adhere on the monoatomic layer or peel off later to form pinholes.

  Thus, in the gas barrier film manufacturing apparatus 50 of the present invention, the processing length L3 of the buffer chamber 64 provided between the first source gas supply chamber 62 and the second source gas supply chamber 63 is the longest. The raw material gas in the first raw material gas supply chamber 62 is prevented from being mixed into the second raw material gas supply chamber 63 and the raw material gas in the second raw material supply chamber 62 is prevented from being mixed into the first raw material gas supply chamber 62. Can do.

  Since the source gas supplied to the first source gas supply chamber 62 and the second source gas supply chamber 63 is usually liquid at normal temperature, it is necessary to supply it by heating and vaporizing. In the example of FIG. 1, each of the first raw material gas supply device 67 and the second raw material gas supply device 68 is configured to have, for example, a cylinder filled with a liquefied raw material and a vaporizer that heats and vaporizes the liquefied raw material. ing. Since the source gas supplied from each source gas supply device 67, 68 may be liquefied if the temperature of the contacting part is low, the first source gas pipe 65, the second source gas pipe 66, the first source gas It is preferable to heat members such as the supply chamber 62, the second source gas supply chamber 63, and the buffer chamber 64 that are in contact with the gas.

  Examples of such heating means include various means such as winding a ribbon heater or a sheathed heater around each gas pipe and installing a thermocouple so that the temperature can be controlled. If the temperature of the member in contact with the gas can be controlled by such heating means, the source gas can be supplied in a stable state. Such a temperature is appropriately set according to the type of the raw material gas and the like, but for example, it is preferably a temperature at which the raw material gas is not liquefied and can be supplied in a state where chemical adsorption or chemical reaction is easy on the base film. Specifically, the temperature is preferably about 30 ° C to 300 ° C.

  The temperatures of the gas pipes are all higher than the temperature at which the raw material gas is vaporized. Further, it is preferable that the temperature of the pipe on the vaporizer side is higher than the temperature of the pipe on the film forming chamber side. However, it is desirable to avoid making the temperature of the gas pipe significantly higher than the temperature at which the raw material is vaporized, because it may cause decomposition of the raw material. For example, when the vaporization temperature of the raw material of the raw material gas is 150 ° C., it is sufficient that the temperature of the gas pipe is 200 ° C. This is due to consideration of temperature variations in the gas piping, temperature measurement errors, and the like.

  As described above, common gas supply pipes 65 and 66 are connected to the first and second source gas supply chambers 62 and 63 provided on the outer periphery of the drum 61, respectively. Further, at least the entire atomic layer deposition apparatus 53 other than the first and second source gas supply chambers 62 and 63 is held in a reduced pressure exhaust atmosphere. With such a configuration, for example, the source gas can be sent from the source gas supply devices 67 and 68 to the supply chamber through one line of piping 65 and 66, respectively, and the device configuration can be simplified. Further, since at least the entire atomic layer deposition apparatus 53 other than the first and second source gas supply chambers 62 and 63 is held in a reduced pressure exhaust atmosphere, there is no need to provide exhaust pipes for each of the many buffer chambers 64. The first and second source gases flowing into the buffer chambers 64 from the first and second source gas supply chambers 62 and 63 can be discharged out of the atomic layer deposition apparatus held in a reduced-pressure exhaust atmosphere. The apparatus configuration can be simplified.

  The supply device 51 is a device that supplies the roll-shaped base film 2 and the storage device 52 is a device that winds up the film 2 ′ after the monoatomic layer stack is formed. You may comprise so that supply operation | movement of the base film 2 by the apparatus 51 and winding operation | movement of the film 2 by the accommodating apparatus 52 may be replaced | exchanged for every fixed time. That is, the supply operation of the base film 2 by the supply device 51 is reversed after a certain period of time, and the drive motor of the supply device 51 is reversed to become a winding device, while the winding operation of the film 2 ′ by the storage device 52 is performed. Then, after a certain time has elapsed, the drive motor of the storage device 52 is reversed so that the supply device is operated. In this way, for example, the base film 2 can be reciprocated between the atomic layer deposition apparatus 53 by roll-to-roll, and as a result, the formation of the monoatomic layer 1 ′ is repeatedly performed to obtain a predetermined thickness. The gas barrier film 1 can be formed.

  The number of processing chambers formed on the drum 61 is not particularly limited, but since the thickness per monoatomic layer is usually about 0.1 nm to 0.5 nm, for example, a monoatomic layer stack of about 30 nm is formed. In order to form a body, it is necessary to execute at least 60 to 300 times of one cycle of [first source gas supply chamber 62 → buffer chamber 64 → second source gas supply chamber 63]. As an example, the processing length L1 of the first source gas supply chamber 62 is 150 mm, the processing length L3 of the buffer chamber 64 is 250 mm, and the processing length L2 of the second source gas supply chamber 63 is 150 mm, as described above. Furthermore, if the thickness of the monoatomic layer is 0.1 nm, a total processing length of about 240 m is required to form a monoatomic layer stack of about 30 nm. For this reason, it is necessary for the atomic layer deposition apparatus 53 to prepare a drum 61 having a diameter of about 100 m, which is not practical. Therefore, the drum 61 is rotated forward and reverse alternately to reduce the substantial processing length. It is necessary to rotate it to about 240 m.

  Accordingly, the number of processing chambers is determined by the thickness per monoatomic layer, the thickness of the final monoatomic layer stack, the length of each processing chamber (L1 to L3), and the like. In the case of a reaction system in which one source gas supply chamber 62 → buffer chamber 64 → second source gas supply chamber 63] is one cycle, a total of 240 to 1200 atomic layer deposition apparatuses in total for each processing chamber 53 can be exemplified.

  Furthermore, the gas barrier film manufacturing apparatus 10 of the present invention may have a configuration other than the above. For example, in order to accelerate the reaction by plasma, high frequency power is applied to the drum 61, and plasma can be generated in each film forming chamber (first source gas supply chamber 62, buffer chamber 64, second source gas supply chamber 63). In addition, an electrode can be installed so that plasma can be generated only in a specific film formation chamber. In this case, the type of plasma is not particularly limited, and various plasmas such as CCP plasma, ICP plasma, microwave plasma, and remote plasma can be used.

  As described above, according to the gas barrier film manufacturing apparatus 10 of the present invention, since it has at least the supply device 51 for the base film 2, the storage device 52 for the film 2 ′, and the monoatomic layer deposition device 53, it is supplied from the supply device 51. A gas barrier film 1 made of a monoatomic layer laminate by an atomic layer deposition method can be produced on the base film 2. In particular, the atomic layer deposition apparatus 53 is not a batch type in which film formation is performed in a single chamber as in the prior art, but a large number of dedicated processing chambers 62 to 64 are continuously arranged on the drum surface for transporting the base film. Therefore, it is possible to save the gas introduction time and exhaust time in each processing chamber, and the productivity can be greatly improved. As a result, the deposition cost of the obtained gas barrier film 2 can be significantly reduced.

[Production method of gas barrier film]
Next, a method for manufacturing a gas barrier film will be described. The method for producing the gas barrier film 1 of the present invention is performed by the gas barrier film production apparatus or the like illustrated in FIG. 1, and continuously moves the long base film 2 on the base film 2. This is a method for producing a gas barrier film 1 by an atomic layer deposition method. This method includes a first source gas supply step for supplying a first source gas for forming a monoatomic layer in a moving direction of the base film 2, and a second source for supplying a second source gas for forming a monoatomic layer. At least three kinds of gas supply steps and a buffer step provided between the first source gas supply step and the second source gas supply step in order to prevent the first source gas and the second source gas from being mixed. It has an atomic layer deposition process in which a large number of steps are continuously arranged. And the gas barrier film 1 which consists of a laminated body of monoatomic layer 1 'can be produced on the base film 2 by allowing the base film 2 to pass through in the atomic layer deposition process.

  This gas barrier film manufacturing method will be described by omitting the same parts as those described above for the gas barrier film manufacturing apparatus.

(Base film)
The base film 2 is not particularly limited as long as it is a long film that can hold the gas barrier film 1 formed by the atomic layer deposition method. Specific constituent materials of the base film include amorphous polyolefin (APO) resin such as cyclic polyolefin, polyester resin such as polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN), polyimide (PI ) Resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, polyarylate (PAR) resin, ethylene- Ethylene tetrafluoride copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), Perfluoro-perfluoropropylene - it can be mentioned perfluoro vinyl ether copolymer (EPA) or the like.

  Moreover, as a constituent material of the base film, in addition to the above resin, a resin composition composed of an acrylate compound having a radical reactive unsaturated compound, a resin composition composed of a mercapto compound having the above acrylate compound and a thiol group, Photocurable resins such as a resin composition in which an oligomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, or methacrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof can also be used. Furthermore, what laminated | stacked 1 type, or 2 or more types of these resin by means, such as a lamination and a coating, can also be used as a base film.

  Among the base films made of the above constituent materials, base films having heat resistance are particularly preferable. The reason is that when the gas barrier film is used for an image display medium, a temperature of 150 ° C. or higher is often applied to the gas barrier film, and at least the glass transition temperature is 60 ° C. or higher, preferably 100 ° C. or higher, more preferably 150 ° C. or higher. It is preferable to use a base film having heat resistance such as

  The thickness of the base film is preferably 3 μm or more and 500 μm or less, and preferably 12 μm or more and 300 μm or less. A base film having a thickness within this range is preferable because it is flexible and can be wound into a roll.

  Although the length of the base film in the longitudinal direction is not particularly limited, since the base film is a long film, for example, a long film of 10 m or more is preferably used. In addition, the upper limit of length is not limited, For example, about 10 km may be sufficient.

(Atomic layer deposition process)
The atomic layer deposition step is a step of forming the gas barrier film 1 by the atomic layer deposition method on the base film 2 described above, specifically, a first source gas supply step, a second source gas supply step, A buffer step for preventing the first source gas and the second source gas from being mixed. A large number of these at least three steps are continuously arranged in the moving direction of the base film 2. By passing the base film 2 through the atomic layer deposition step, the gas barrier film 1 composed of a laminate of the monoatomic layer 1 ′ can be produced on the base film 2. Since the atomic layer deposition method has been described above, the description thereof is omitted here.

The first source gas supply step is a step of supplying a first source gas for forming a monoatomic layer. As the first source gas, various source gases applicable to the atomic layer deposition method can be used. Among these, any compound gas selected from Al compound gas, Zr compound gas, Hf compound gas, and the like, which are source gases of Al ₂ O ₃ , ZrO ₂ , and HfO ₂ that can be formed at a low temperature is preferable.

Specifically, examples of the Al compound gas include organometallic compound gases such as trimethylaluminum (TMA) gas, triethylaluminum (TEA) gas, dimethylaluminum hydride (DMAH) gas, and inorganic metal compound gases such as aluminum chloride gas. be able to. Examples of the Zr compound gas include organic metal compound gases such as Zr (OtBu) ₄ gas and tetra-t-butoxyzirconium Zr (Ot—C ₄ H ₉ ) ₄ , and inorganic metal compound gases such as zirconium chloride gas. Can do. As the Hf compound gas, organometallic compound gas such as Hf (OtBu) ₄ gas, Hf (NMe ₂ ) ₄ gas, tetra t-butoxyhafnium Hf (Ot—C ₄ H ₉ ) ₄ , hafnium tetrachloride, etc. Inorganic metal compound gas can be mentioned.

The second source gas supply step is a step of supplying a second source gas for forming a monoatomic layer. As the second source gas, for example, when forming the above-described low-temperature filmable Al ₂ O ₃ , ZrO ₂ , HfO ₂ or the like, any one selected from a water vapor-containing gas, an oxygen-containing gas, and an ozone-containing gas is used. These gases are preferably used.

  Note that the first source gas and the second source gas are supplied from the first source gas supply device 67 through the first source gas pipe 65, as illustrated in FIG. For example, a method of supplying the first raw material gas supply chamber 62 to the second raw material gas supply chamber 63 from the second raw material gas supply device 68 through the second raw material gas pipe 66 can be exemplified.

  In order to prevent the first source gas from being mixed into the second source gas supply step and the second source gas from being mixed into the first source gas supply step, the buffering step includes the first source gas supply step and the second source gas supply step. It is a step provided between the source gas supply step. This buffering step leads the base film 2 to a reduced pressure exhaust atmosphere, and as a result, acts to remove excess source gas adhering to the base film 2 under a reduced pressure exhaust atmosphere.

  If these steps are specifically shown in the example of FIG. 1, the first source gas supply step → buffer step → second source gas supply step → buffer step → first source gas supply step → buffer step → …… → A large number are successively arranged in the order of buffer step → second source gas supply step. Note that one cycle in which the monoatomic layer 1 ′ is formed is “first source gas supply step → buffer step → second source gas supply step”, and is configured to be sequentially continued with the buffer step interposed therebetween.

By such a monoatomic layer deposition step, a monoatomic layer 1 ′ is formed every cycle, and by arranging a large number of the cycles in the moving direction of the base film 2, a monoatomic layer 1 ′ stack can be formed. it can. By selecting the first source gas and the second source gas from the above source gases, for example, any gas barrier film 1 selected from Al ₂ O ₃ , ZrO ₂ , and HfO _{2 that} can be formed at a low temperature can be produced. .

  In the above, the three steps of the first source gas supply step, the second source gas supply step, and the buffer step have been described. However, this monoatomic layer deposition step is not limited to these three steps, Depending on the composition of the layer, the third source gas supply step may be provided via a buffer step, and further the fourth source gas supply step may be provided via a buffer step.

  In this monoatomic layer deposition process, the processing time in the first source gas supply step is T1, the processing time in the second source gas supply step is T2, the processing time in the buffer step is T3, and the raw material to each processing step When the gas supply pressure is the same for both the first source gas and the second source gas, it is preferable that the relationship between the processing times is T3> T1 ≧ T2, preferably T3> T1> T2. .

  Specifically, it is the same as that described in the gas barrier film manufacturing apparatus 50 described above, “processing length L” is read as “processing time T”, and “supply chamber” and “buffer chamber” are “supply step”. And “buffer step” can be described in the same manner as described above, and will be briefly described here.

  Regarding the relationship between the processing time T1 of the first source gas supply step and the processing time T2 of the second source gas supply step, when the supply pressure P1 of the first source gas and the supply pressure P2 of the second source gas are the same, The processing time T1 of the first source gas supply step is longer than the processing time T2 of the second source gas supply step (T1 ≧ T2), preferably longer than the processing time T2 (T1> T2). When the supply pressure P1 of the first source gas and the supply pressure P2 of the second source gas are different, the relationship between the processing times T1 and T2 when the pressure is taken into consideration is [P1 × T1] ≧ [P2 × T2 ], Preferably [P1 × T1]> [P2 × T2].

  Next, a case where the buffer step processing time T3 is also considered will be described. Since the adsorption reaction of the first source gas on the base film 2 is completed immediately and the chemical reaction of the second source gas on the base film 2 is also completed immediately, the first source gas supply step The processing time T1 and the processing time T2 of the second source gas supply step may be short. On the other hand, the buffering step needs to have a longer processing time T3 so that the raw material gases from the two adjacent supply steps enter the other raw material gas supply steps and do not react. Therefore, as described above, T3> T1 ≧ T2, preferably T3> T1> T2.

  Although the number of the above processing steps is not particularly limited, the thickness per monoatomic layer is usually about 0.1 nm to 0.5 nm, as described in the atomic layer deposition apparatus 53 above. For example, in order to form a monoatomic layer stack of about 30 nm, it is necessary to execute at least 60 to 300 times of one cycle of [first source gas supply step → buffer step → second source gas supply step]. . As an example, the processing time T1 of the first source gas supply step is 3 seconds, the processing time T3 of the buffer step is 5 seconds, the processing time T2 of the second source gas supply step is 3 seconds, and the thickness of the monoatomic layer If the thickness is 0.1 nm, in order to form a monoatomic layer stack having a thickness of about 30 nm, the atomic layer deposition process requires about 80 minutes as the total processing time.

  Accordingly, the number of processing steps is determined by the thickness per monoatomic layer, the final thickness of the monoatomic layer stack, the processing time (T1 to T3) of each processing step, and the like, for example, In the case of a reaction system in which one source gas supply step → buffer step → second source gas supply step] is one cycle, an atomic layer deposition step of 240 steps or more and 1200 steps or less can be exemplified in total for each processing step. .

  As described above, according to the method for producing a gas barrier film of the present invention, a monoatomic layer laminate by an atomic layer deposition method is formed on a base film by continuously moving a long base film in the atomic layer deposition step. Since the gas barrier film made of can be produced, productivity can be greatly improved. In addition, since gas introduction time and exhaust time can be saved, productivity can be greatly improved compared to gas barrier films obtained by conventional atomic layer deposition methods, and the gas barrier film deposition costs are significantly reduced. Can be made.

[Gas barrier film]
Next, the gas barrier film of the present invention will be described. The gas barrier film of the present invention is produced by the gas barrier film production method according to the present invention or the gas barrier film production apparatus according to the present invention. As shown in FIG. A gas barrier film 1 made of a laminate of a monoatomic layer 1 ′ is provided. Since the gas barrier film 1 and the base film 2 constituting the gas barrier film 3 are as described above, the description thereof is omitted here.

  The obtained gas barrier film 3 has a dense and uniform laminate of the monoatomic layer 1 ′ as the gas barrier film 1 on the base film 2, so that the base film 2 is difficult to avoid. Even if it exists, the gas barrier film 1 made of a uniform and dense monoatomic layer laminate along the irregularities and defects of the base film 2 is obtained more efficiently and at a lower cost than before.

  In the gas barrier film 3 of the present invention, a protective film (not shown) may be provided on the gas barrier film 1, or a gas barrier film (not shown) formed by another method on the opposite surface of the base film 2. ) May be formed. Such a protective film and a gas barrier film formed by other methods can be formed in various conventionally known forms. For example, examples of the protective film include those having a smooth surface and acid resistance, and those having gas barrier properties, but are not particularly limited. The protective film can be formed of an inorganic compound by a sputtering method, an ion plating method, a CVD method, or the like, and an organic compound can be formed by a coating method, a vapor deposition method, or the like. In addition, a gas barrier film formed by another method can be formed by sputtering, ion plating, CVD, or the like using an inorganic compound known to have gas barrier properties. Further, an organic compound known to have gas barrier properties can be formed by a coating method or the like.

  In addition, an anchor coat layer may be formed between the base film 2 and the gas barrier film 1 for preventing the gas barrier film 1 from being formed and improving the adhesion between them. Examples of the material for the anchor coat layer include resins such as acrylic, and an additive may be added as necessary. Usually, it is formed by applying and drying by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating.

The gas barrier film 3 of the present invention is a uniform and dense monoatomic layer along the unevenness and defects of the base film 2 even when the unevenness of the base film 2 and defects due to foreign matters exist that are difficult to avoid. Since the gas barrier film 1 made of a laminate is formed, the oxygen transmission rate and water vapor transmission rate can be set to preferable levels, and at least the oxygen transmission rate is 1 cc / m ² / day · atm or less and the water vapor transmission rate is low. 1 g / m ² / day or less, preferably an oxygen permeability of 0.1 cc / m ² / day · atm or less and a water vapor transmission rate of 0.1 g / m ² / day or less to exhibit extremely excellent gas barrier properties .

  The gas barrier film of the present invention having such a gas barrier property can be applied to various uses, for example, for liquid crystal display panels, organic EL display panels, solar cells, packaging materials such as electronic devices, foods and pharmaceuticals, etc. It can be used for packaging materials.

  Next, an Example is shown and this invention is demonstrated further in detail.

Example 1
A gas barrier film having an Al ₂ O ₃ film as a gas barrier film was manufactured using the gas barrier film manufacturing apparatus 50 shown in FIG. First, a roll of a polyethylene naphthalate (PEN) film having a thickness of 100 μm, a width of 30 cm, and a length of 1 km was attached to the supply device 51 as a base film 2. Next, the tip of the base film 2 is pulled out while being rotated in contact with the surface of the drum 61 of the atomic layer deposition device 53, and fixed to the core material 14 of the storage device 52 having a winding function to wind up. The conveyance was started while rotating the base film 2 at a constant speed of 20 m / min. In that state, a monoatomic layer laminate was prepared on the base film 2 by an atomic layer deposition method. The drum 61 was heated and controlled using a heat medium discharged from a chiller (cooler) so that the temperature of the base film 2 was 80 ° C.

  The atomic layer deposition apparatus 53 for forming the monoatomic layer stack is arranged on the drum 61 having a diameter of 1 m from the supply side, from the first source gas supply chamber 62 → the buffer chamber 64 → the second source gas supply chamber 63 → the buffer chamber 64. → 11 first source gas supply chamber 62 → buffer chamber 64 → second source gas supply chamber 63 → buffer chamber 64 → first source gas supply chamber 62 → buffer chamber 64 → second source gas supply chamber 63 It is an apparatus provided with a chamber, and is an apparatus provided with three cycles of one cycle for forming the monoatomic layer 1 ′. At this time, the processing length L1 of the first source gas supply chamber 62 is 15 cm (the processing time T1 is 0.45 seconds at the transfer speed of 20 m / min), and the processing of the second source gas supply chamber 63 is performed. The length L2 is 15 cm (the processing time T2 is 0.45 seconds at the transfer speed of 20 m / min), and the processing length L3 of the buffer chamber 64 is 25 cm (the transfer speed is 20 m / min at the transfer speed of 20 m / min. Time T3 is 0.75 seconds).

Al (CH ₃ ) ₃ gas having a pressure of 10 Pa as the first source gas is supplied from the first source gas supply device 67 to each first source gas supply chamber 62 via the first source gas pipe, and the second source gas is supplied. H ₂ O gas having a pressure of 10 Pa was supplied from the second source gas supply device 68 to the second source gas supply chamber 63 via the second source gas pipe. Further, the entire apparatus 50 is reduced to 0.01 Pa by the decompression device 73 so that the first source gas and the second source gas flowing into the buffer chamber 64 are not mixed into the other source gas supply chambers. Was exhausted.

In such an apparatus 50, the film formation time for one pass on a film having a width of 0.3 m and a length of 100 m is 5 minutes, and three layers (about 0.3 nm) are formed at that time. In order to form a film with a thickness of 20 nm, it is necessary to pass the film 67 times, and the film formation time at that time is 5.6 hours. The film formation time per unit area is 0.19 hours / m ² .

Thus, the gas barrier film 3 of Example 1 in which the Al ₂ O ₃ film, which is a monoatomic layer laminate, was formed on the base film 2 was obtained. This gas barrier film 3 had an oxygen transmission rate of 0.1 cc / m ² / day and a water vapor transmission rate of 0.1 g / m ² / day. The oxygen permeability was measured using an oxygen gas permeability measuring device (OX-TRAN 2/20 manufactured by MOCON) under the conditions of a temperature of 23 ° C. and dry (0% RH). In addition, the measurement was performed by the measurement method “with independent zero” that removes the background. On the other hand, the water vapor transmission rate was measured using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON) under conditions of a temperature of 37.8 ° C. and a humidity of 100% RH.

(Comparative Example 1)
A gas barrier film having an Al ₂ O ₃ film as a gas barrier film was produced using a batch-type atomic layer deposition apparatus. A polyethylene naphthalate (PEN) film having a thickness of 100 μm and a length of 30 cm × width of 30 cm was prepared as a base film and placed in a film formation chamber of about 40 cm × 40 cm square. The temperature was adjusted so that the temperature of the base film was 80 ° C.

In the formation of the monoatomic layer stack, first, Al (CH ₃ ) ₃ gas is filled as a first source gas into the chamber from the first source gas supply device via a dedicated pipe, and Al (CH) is formed on the base film. CH ₃ ) ₃ gas was chemisorbed. Next, Al (CH ₃ ) ₃ gas in the chamber was exhausted from the dedicated pipe by an exhaust device. Next, as a second source gas, H ₂ O gas is filled into the chamber from the second source gas supply device via a dedicated pipe and chemically reacted with Al (CH ₃ ) ₃ adsorbed on the base film. A monoatomic Al ₂ O ₃ film was formed. Next, the H ₂ O gas in the chamber was exhausted from the dedicated pipe by an exhaust device. Thereafter, Al (CH ₃ ) ₃ gas filling → Al (CH ₃ ) ₃ gas evacuation → H ₂ O gas filling → H ₂ O gas evacuation is repeated to repeat Al ₂ O ₃ as a monoatomic layer stack. A film was formed. Each gas switching time was 2 seconds for gas introduction and 2 seconds for gas exhaust. The film formation time per unit area was about 1.9 hours / m ² and the film formation time was about 10 minutes.

In this way, a 20 nm thick Al ₂ O ₃ film as a monoatomic layer laminate was formed on the base film, and the gas barrier film of Comparative Example 1 was obtained. This gas barrier film had an oxygen transmission rate of 0.1 cc / m ² / day and a water vapor transmission rate of 0.1 g / m ² / day. The oxygen permeability and water vapor permeability were measured in the same manner as in Example 1.

(Comparative Example 2)
A gas barrier film having an Al ₂ O ₃ film as a gas barrier film was produced using an EB vacuum deposition apparatus. This EB vacuum vapor deposition device is a device consisting of a film formation chamber, an exhaust pump, a vapor deposition crucible, and an EB gun. A polyethylene naphthalate (PEN) film having a thickness of 100 μm and a thickness of 200 mm × 300 mm is supplied to the device as a base film. Then, a gas barrier film made of Al ₂ O ₃ having a thickness of 20 nm was formed.

As the film formation conditions in the EB vacuum vapor deposition apparatus, Al was used as the vapor deposition material, O ₂ gas was used as the raw material gas, and the film was formed under the condition of a film formation pressure of 10 ⁻³ Pa under the condition of 0.5 nm / second. . The film formation time per unit area in this EB vacuum deposition apparatus was about 0.19 hours / m ² , and the film formation time was about 0.7 minutes.

Thus, an Al ₂ O ₃ film was formed on the base film, and a gas barrier film of Comparative Example 2 was obtained. This gas barrier film had an oxygen transmission rate of 1.0 cc / m ² / day and a water vapor transmission rate of 1.1 g / m ² / day. The oxygen permeability and water vapor permeability were measured in the same manner as in Example 1.

(Evaluation)
Since the gas barrier film of Example 1 and the gas barrier film of Comparative Example 1 were formed by the atomic layer deposition method, both had low oxygen permeability and water vapor permeability, and had excellent gas barrier properties. However, as the formation efficiency of the gas barrier film, the film formation time of 0.19 hours per unit area in Example 1 was compared with 1.9 hours of film formation time per unit area in Comparative Example 1. Example 1 was remarkably superior in terms of production efficiency. In Comparative Example 1, A 20 nm thick gas barrier film is formed on a 30 cm × 30 cm base film in 10 minutes. As in Example 1, a 20 nm thick gas barrier film is formed in the same area as the 30 cm × 100 m base film. Then, it takes about 56 hours, which is 10 times that of Example 1. Moreover, since the gas barrier film of Comparative Example 2 formed a gas barrier film by the EB vacuum deposition method, it was remarkably inferior to the atomic layer deposition methods of Example 1 and Comparative Example 1 in terms of gas barrier properties.

It is a typical block diagram which shows an example of the production apparatus of the gas barrier film of this invention. It is a cross-sectional block diagram which shows an example of the gas barrier film obtained by the preparation apparatus which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier film 1 'Monoatomic layer 2 Base film 2' Film 3 Gas barrier film 50 Gas barrier film production apparatus 51 Supply apparatus 52 Storage apparatus 53 Atomic layer deposition apparatus 54,55 Guide roller 56 Damper 61 Drum 62 1st source gas supply Chamber 63 Second source gas supply chamber 64 Buffer chamber 65 First source gas pipe 66 Second source gas pipe 67 First source gas supply device 68 Second source gas supply device 69 Opening 71 Chamber 72 Reduced pressure atmosphere 73 Reduced pressure device L1 First 1 Processing length of source gas supply chamber L2 Processing length of second source gas supply chamber L3 Processing length of buffer chamber T1 Processing time of first source gas supply chamber T2 Processing time of second source gas supply chamber T3 Buffer chamber Processing time

Claims (8)

A method of producing a gas barrier film composed of a monoatomic layer laminate by atomic layer deposition on the base film while continuously moving a long base film,
In the direction of movement of the base film,
A first source gas supply step of supplying any compound gas selected from Al compound gas, Zr compound gas, and Hf compound gas, which is a first source gas for forming a monoatomic layer, to the first source gas supply chamber;
A second source gas supply step of supplying any gas selected from a water vapor-containing gas, an oxygen-containing gas, and an ozone-containing gas, which is a second source gas for forming a monoatomic layer, to the second source gas supply chamber;
A buffer chamber is provided between the first source gas supply chamber and the second source gas supply chamber, and the buffer chamber is placed in a reduced pressure exhaust atmosphere to thereby provide the first source gas supply chamber and the second source gas supply chamber. A buffering step for removing the first source gas and the second source gas leaked from
Have at least three formed by arranging a large number of steps continuously atomic layer deposition process having,
The supply pressure P1 of the first source gas, the supply pressure P2 of the second source gas, the processing time T1 in the first source gas supply step, and the processing time T2 in the second source gas supply step A method for producing a gas barrier film, wherein the relationship is [P1 × T1] ≧ [P2 × T2] .   The relationship between the processing time T1 in the first source gas supply step, the processing time T2 in the second source gas supply step, and the processing time T3 in the buffer step is T3> T1 ≧ T2. Item 2. A method for producing a gas barrier film according to Item 1. The method for producing a gas barrier film according to claim 1 or 2 , wherein the monomolecular layered product is any one selected from Al ₂ O ₃ , ZrO ₂ , and HfO ₂ . An apparatus for producing a gas barrier film composed of a monoatomic layer laminate by an atomic layer deposition method on a base film while continuously moving a long base film,
A supply device for supplying the base film;
A housing device for housing the base film after forming the monoatomic layer stack;
Having at least a monoatomic layer deposition device for depositing a monoatomic layer provided between the supply device and the containing device;
The monoatomic layer deposition apparatus comprises:
A drum that conveys the substrate film in contact with the surface at a constant speed;
A first source gas supply chamber for supplying any compound gas selected from Al compound gas, Zr compound gas and Hf compound gas, which is a first source gas for forming a monoatomic layer, provided on the outer periphery of the drum When,
A second source gas supply chamber for supplying any gas selected from water vapor-containing gas, oxygen-containing gas and ozone-containing gas, which is a second source gas for forming a monoatomic layer, provided on the outer periphery of the drum; ,
The first source gas supply chamber and the second source gas supply chamber are provided between the first source gas supply chamber and the second source gas supply chamber on the outer periphery of the drum, and are in a reduced pressure exhaust atmosphere. A buffer chamber for removing the first source gas and the second source gas leaked from
Ri Na arranged many consecutive at least three processing chambers having,
The supply pressure P1 of the first source gas, the supply pressure P2 of the second source gas, the process length L1 of the first source gas supply chamber, and the process length L2 of the second source gas supply chamber The apparatus for producing a gas barrier film , wherein the first source gas supply chamber and the second source gas supply chamber are configured so that the relationship is [P1 × L1] ≧ [P2 × L2] . The relationship between the processing length L1 of the first source gas supply chamber, the processing length L2 of the second source gas supply chamber, and the processing length L3 of the buffer chamber is L3> L1 ≧ L2. Item 5. A gas barrier film manufacturing apparatus according to Item 4 . A common gas supply pipe is connected to each of the first and second source gas supply chambers provided on the outer periphery of the drum,
The apparatus for producing a gas barrier film according to claim 4 or 5 , wherein at least the entire atomic layer deposition apparatus other than the first and second source gas supply chambers is held in a reduced pressure exhaust atmosphere. The apparatus for producing a gas barrier film according to any one of claims 4 to 6 , wherein the first source gas supply chamber, the second source gas supply chamber, and the drum are heated by a heating unit. The supply device is a device for supplying a roll-shaped base film, and the accommodation device is a device for winding the base film after the monoatomic layer laminate is formed, and the base material by the supply device The apparatus for producing a gas barrier film according to any one of claims 4 to 7 , wherein the film supply operation and the winding operation of the base film by the accommodation device are switched at regular intervals.

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