JPWO2016117625A1 - Gas barrier film manufacturing method and manufacturing apparatus - Google Patents

Abstract

A method for producing a gas barrier film capable of further improving the barrier properties is provided. An adjustment step of adjusting the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas in the discharge space P when forming a barrier film 3 to be 0.05 or more and 1.0 or less is provided. . [Selection] Figure 2

Description

  The present invention relates to a gas barrier film manufacturing method and manufacturing apparatus.

  In recent years, gas barrier films that prevent permeation of water vapor, oxygen, and the like have been requested to be developed into electronic devices such as organic electroluminescence (EL) elements and liquid crystal display (LCD) elements, and many studies have been made. In these electronic devices, flexibility is required, and further thinning of the base material is required.

  However, if the thickness of the base material is too thin, curling due to the stress of the barrier film formed on the base material tends to occur, which is not preferable. On the other hand, if the barrier film is made too thin, the problem of curling is improved. However, since the thickness of the barrier film is small, even a minute defect can be a passage through which moisture passes. Is likely to occur.

  In this connection, for example, Patent Document 1 below discloses a barrier film having improved flexibility by continuously changing the carbon component to have an extreme value in the range of 3 to 33%. Yes.

JP 2011-73430 A

  However, it has been found that the technique of Patent Document 1 still has insufficient barrier properties.

  This invention is made | formed in order to solve said subject, and it aims at providing the manufacturing method and manufacturing apparatus of a gas barrier film which can improve barrier property further.

  The method for producing a gas barrier film according to the present invention that achieves the above object includes a first film forming roll that stretches a substrate while supplying a source gas containing at least carbon and a reaction gas containing oxygen gas into a vacuum chamber. And a high-frequency voltage applied to the second film forming roll that is disposed opposite to the first film forming roll by a predetermined distance and stretches the base material that has passed through the first film forming roll. A method for producing a gas barrier film by plasma CVD, wherein a barrier film is formed on the surface of the substrate in a discharge space formed between the first film-forming roll and the second film-forming roll by applying An adjustment step of adjusting the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space to be 0.05 or more and 1.0 or less when forming the barrier film. Have.

  In addition, a gas barrier film manufacturing apparatus according to the present invention that achieves the above-described object provides a first component for stretching a substrate while supplying a source gas containing at least carbon and a reaction gas containing oxygen gas into a vacuum chamber. A high frequency with respect to the film roll and the second film forming roll that faces the first film forming roll and is opposed to the first film forming roll by a predetermined distance and stretches the base material that has passed through the first film forming roll. A gas barrier film formed by a plasma CVD method that applies a voltage to form a barrier film on the surface of the substrate in a discharge space formed between the first film forming roll and the second film forming roll. Adjustment that adjusts the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas in the discharge space to be 0.05 or more and 1.0 or less when the barrier film is formed in the manufacturing apparatus Have means That.

It is front sectional drawing which shows the gas barrier film which concerns on embodiment of this invention. It is a figure which shows the manufacturing apparatus of the gas barrier film which concerns on 1st Embodiment of this invention. It is a figure which shows the manufacturing apparatus of the gas barrier film which concerns on 2nd Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.

  FIG. 1 is a front sectional view showing a gas barrier film 1 according to an embodiment of the present invention. As shown in FIG. 1, a gas barrier film 1 according to an embodiment of the present invention includes a barrier film 3 on one side of a substrate 2. An overcoat layer (not shown) may be provided on the barrier film 3 for the purpose of protecting the barrier film 3, smoothing, improving adhesiveness, and the like. Furthermore, in addition to the above-described configuration, the gas barrier film 1 may be provided with various conventionally known layers as required. For example, between the base material 2 and the barrier film 3, an anchor coat layer, A smooth layer, a bleed-out prevention layer (both not shown) and the like can be exemplified, but are not limited thereto.

  Although it does not restrict | limit especially as the base material 2, Flexibility (flexibility), mechanical strength (For example, durability at the time of conveyance by roll-to-roll, etc.), and also a solar cell or an electronic component Thus, the film or sheet which consists of resin which has durability when a temperature change arises is preferable, More preferably, it is the film or sheet which consists of colorless and transparent resin which has the said characteristic. Examples of the resin used for the substrate 2 include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin. A polyamide resin; a polycarbonate resin; a polystyrene resin; a polyvinyl alcohol resin; a saponified ethylene-vinyl acetate copolymer; a polyacrylonitrile resin; an acetal resin; and a polyimide resin. Among these resins, polyester resins and polyolefin resins are preferred, and PET and PEN are particularly preferred from the viewpoints of high heat resistance and linear expansion coefficient and low production cost. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the base material 2 can be appropriately set in consideration of stability and mechanical strength (for example, durability at the time of roll-to-roll conveyance) when the gas barrier film 1 is manufactured. The thickness of the base material 2 is 5 from the viewpoints of flexibility (flexibility), stability during production, and mechanical strength (for example, a film can be conveyed in a roll-to-roll manner even in a vacuum). It is preferably in the range of ˜500 μm. Furthermore, since the barrier film 3 is formed while discharging through the base material 2, the thickness of the base material 2 is more preferably in the range of 50 to 200 μm, and particularly preferably in the range of 50 to 100 μm.

  Further, from the viewpoint of adhesion to the barrier film 3, the substrate 2 is preferably subjected to surface activation treatment for cleaning the surface of the substrate. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

  The barrier film 3 is a layer formed on one side of the substrate 2. In the gas barrier film 1, the barrier film 3 is not particularly limited as long as it has a barrier property, but is preferably a layer containing silicon, oxygen and carbon. The barrier film 3 may further contain nitrogen and aluminum.

  When the barrier film 3 contains silicon, oxygen, and carbon, the effect of the present invention is effective as the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier film 3. It may be within the range that can be expressed in the range of 20 to 50 at%, preferably 25 to 45 at%, more preferably 30 to 40 at%. If the atomic ratio of the silicon atom content is 20 at% or more, preferably 25 at% or more, it is preferable in that the performance fluctuation with time is small and the high barrier performance of silicon can be effectively expressed. If the atomic ratio of the content of silicon atoms is 50 at% or less, preferably 45 at% or less, in addition to excellent moisture resistance, high barrier performance can be effectively expressed without impairing flexibility and flexibility. preferable.

  The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the barrier film 3 may be within a range in which the effects of the present invention can be effectively expressed, and is 30 to 70 at%. The range is preferably 33 to 67 at%, more preferably 40 to 67 at%. If the atomic ratio of the oxygen atom content is 30 at% or more, in addition to excellent transparency, a gas barrier film excellent in durability when the film is bent or when temperature changes occur like a solar cell or an electronic component. It is preferable in that it can effectively provide high barrier performance without impairing flexibility, flexibility, durability due to temperature change, and the like. If the atomic ratio of the oxygen atom content is 70 at% or less, there is little performance fluctuation over time, and it is excellent in durability when a film is bent or when a temperature change occurs like a solar cell or an electronic component. It is preferable in that a high barrier performance can be effectively expressed without impairing flexibility, flexibility, durability due to temperature change, and the like, such as providing a gas barrier film.

  The atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the barrier film 3 may be within a range in which the effects of the present invention can be effectively expressed. The range is 40 at%, preferably 3 to 33 at%, more preferably 5 to 30 at%. If the atomic ratio of the carbon atom content is 0.5 at% or more, the gas barrier has excellent flexibility and durability when the film is bent or when temperature changes occur such as in solar cells and electronic parts. It is preferable in that a high barrier performance can be effectively expressed without impairing flexibility, flexibility, durability due to temperature change, and the like, such as being able to provide a film. If the atomic ratio of the carbon atom content is 40 at% or less, in addition to excellent transparency, it is possible to suppress an increase in film defects without sacrificing flexibility, flexibility, durability due to temperature changes, etc. It is preferable at the point which can express high barrier performance effectively.

  Next, the manufacturing apparatus 100 of the gas barrier film 1 which concerns on 1st Embodiment for manufacturing the gas barrier film 1 mentioned above is demonstrated.

<First Embodiment>
FIG. 2 is a view showing the gas barrier film 1 manufacturing apparatus 100 according to the first embodiment of the present invention.

  The manufacturing apparatus 100 for the gas barrier film 1 according to the first embodiment can be summarized as a first method for stretching the substrate 2 while supplying a source gas containing carbon and a reaction gas containing oxygen gas into the vacuum chamber 80. A film forming roll 19 and a second film forming roll 20 that stretches the substrate 2 that is disposed to be opposed to the first film forming roll 19 at a predetermined distance and pass through the first film forming roll 19. On the other hand, plasma CVD is performed by applying a high-frequency voltage to form a barrier film 3 on the surface of the substrate 2 in the discharge space P formed between the first film-forming roll 19 and the second film-forming roll 20. It is the manufacturing apparatus 100 of the gas barrier film 1 by a method. The manufacturing apparatus 100 adjusts so that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P when forming the barrier film 3 is 0.05 or more and 1.0 or less. Have Hereinafter, the configuration of the manufacturing apparatus 100 according to the present embodiment will be described in detail.

  The gas barrier film 1 manufacturing apparatus 100 according to the first embodiment includes a delivery roll 14, transport rolls 15, 16, 17, 18, a take-up roll 25, film forming rolls 19, 20, and a plasma generation power source 22. , Magnetic field generators 23, 24, source gas supply port 31, source gas supply unit 32, reaction gas supply port 41, reaction gas supply unit 42, vacuum chamber 80, vacuum pump 81, and adjusting means. 50 and measuring means 60.

  The delivery roll 14 delivers the base material 2. Further, the transport rolls 15, 16, 17, 18 transport the base material 2 sent out by the feed roll 14 to the take-up roll 25. The take-up roll 25 takes up the gas barrier film 1 in which the barrier film 3 is formed on the substrate 2.

  As the delivery roll 14, the transport rolls 15, 16, 17, 18, and the take-up roll 25, known rolls can be used as appropriate.

  The film forming rolls 19 and 20 are arranged to face each other, and the barrier film 3 is formed on the substrate 2 in the discharge space P between the film forming rolls 19 and 20. In order for the film forming rolls 19 and 20 to function as a pair of counter electrodes, a plasma generating power source 22 is connected to each of the film forming rolls 19 and 20. For this reason, it is possible to discharge to the discharge space P between the first film-forming roll 19 and the second film-forming roll 20 by supplying electric power from the plasma generation power source 22, and the reaction gas is Plasma can be generated in the supplied discharge space P.

  Further, in such a plasma CVD method, a film forming roll connected to a plasma generating power source 22 for discharging in the discharge space P between the first film forming roll 19 and the second film forming roll 20. The electric power applied to 19 and 20 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber 80, etc., and cannot be generally stated, but should be in the range of 0.1 to 10 kW. Is preferred. If such an applied power is 0.1 kW or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated during film formation can be suppressed. It can suppress that the temperature of the surface of the base material 2 rises. For this reason, it is excellent at the point which can prevent generating a wrinkle at the time of film formation, without the base material 2 losing heat.

  Note that the first film-forming roll 19 and the second film-forming roll 20 are preferably arranged so that their central axes are substantially parallel on the same plane. By arranging the film forming rolls 19 and 20 in this way, the film forming rate can be doubled as compared with the plasma CVD method using no roll.

  Inside the first film-forming roll 19 and the second film-forming roll 20, magnetic field generators 23 and 24 fixed so as not to rotate even when the film-forming rolls 19 and 20 rotate are provided, respectively. Yes.

  The magnetic field generators 23 and 24 do not straddle magnetic lines of force between the magnetic field generator 23 provided on the first film-forming roll 19 and the magnetic field generator 24 provided on the second film-forming roll 20. The magnetic poles are preferably arranged so that each magnetic field generator 23, 24 forms a substantially closed magnetic circuit. By arranging the magnetic field generators 23 and 24 in this way, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surfaces of the film forming rolls 19 and 20, and the plasma is converged on the bulging portion. Since it becomes easy, the film-forming efficiency can be improved.

  The magnetic field generators 23 and 24 are each provided with a racetrack-shaped magnetic pole that is long in the roll axis direction, and the magnetic poles are arranged so that the magnetic poles facing one magnetic field generator 23 and the other magnetic field generator 24 have the same polarity. It is preferable to arrange. By arranging the magnetic field generators 23 and 24 in this way, the respective magnetic field generators 23 and 24 are discharged along the length direction of the roll axis without straddling the magnetic field generator on the roll side where the magnetic lines of force oppose each other. A racetrack-like magnetic field can be easily formed in the vicinity of the surfaces of the film forming rolls 19 and 20 facing the space P, and plasma can be converged on the magnetic field, so that it is wound along the roll width direction. It is excellent in that the film can be efficiently formed using the wide base material 2.

  As the film forming rolls 19 and 20, known rolls can be used as appropriate. As such film forming rolls 19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming the barrier film 3 more efficiently. Further, the diameter of the film forming rolls 19 and 20 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the film forming rolls 19 and 20 have a diameter of 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated, and it is possible to avoid the total amount of plasma discharge from being applied to the substrate 2 in a short time. Therefore, damage to the substrate 2 can be reduced, which is preferable. On the other hand, if the diameter of the film forming roll is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of device design including uniformity of plasma discharge space.

  Moreover, the base material 2 is arrange | positioned so that the surface of the base material 2 may oppose on the film-forming rolls 19 and 20, respectively. By disposing the substrate 2 in this way, when the discharge space P between the first film forming roll 19 and the second film forming roll 20 is discharged to generate plasma, the film forming roll 19, The barrier film 3 can be simultaneously formed on each surface of the substrate 2 on the substrate 20. Therefore, since the barrier film 3 can be formed on each of the film forming rolls 19 and 20, the film can be formed more efficiently.

  As the plasma generating power source 22, a known power source for a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 22 supplies power to the film forming rolls 19 and 20 connected to the plasma generating power supply 22 and uses the film forming rolls 19 and 20 as counter electrodes for discharging. Make it possible. As such a plasma generation power source 22, a power source (AC power source or the like) that can alternately reverse the polarities of the film forming rolls 19 and 20 is used in order to perform plasma CVD more efficiently. preferable. Moreover, as such a plasma generation power supply 22, in order to implement plasma CVD more efficiently, it is preferable that applied electric power shall be 100 W-10 kW, and AC frequency shall be 50 Hz-500 kHz. As the magnetic field generators 23 and 24, known magnetic field generators can be used as appropriate.

  The source gas supply port 31 supplies the source gas stored in the source gas supply unit 32 provided outside the vacuum chamber 80 into the discharge space P. The source gas stored in the source gas supply unit 32 is supplied into the discharge space P by a vaporizer or a bubbler. The source gas supply port 31 is preferably provided on one side (the upper side in FIG. 2) of the discharge space P, and a vacuum pump 81 described later is preferably provided on the other side (the lower side in FIG. 2) of the discharge space P. Thus, the source gas supply port 31 and the vacuum pump 81 are arranged to face each other via the discharge space P, whereby the source gas can be efficiently supplied to the discharge space P, and the film formation efficiency is improved. Can do.

  As the source gas supplied to the discharge space P, for example, an organic silicon compound containing carbon and silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of properties such as compound handling properties and gas barrier properties of the resulting barrier film. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, acetylene, tetraisopropyl titanate, titanium tetraethoxide, titanium tetrabutoxide, cyclopentadinier titanium triisopropoxide, tetrakisdimethylamino titanium, Examples thereof include tetrakisdiethylaminotitanium, tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, tetra-n-butoxyaluminum, and aluminum sec-butyrate. In particular, aluminum sec-butyrate and tetraisopropyl titanate are preferable. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the barrier film 3.

  The reaction gas supply port 41 supplies the reaction gas stored in the reaction gas supply unit 42 provided outside the vacuum chamber 80 into the discharge space P. The reactive gas supply unit 42 is, for example, a cylinder that stores reactive gas. The reactive gas supply port 41 is preferably provided on one side of the discharge space P (upper side in FIG. 2), and a vacuum pump 81 described later is preferably provided on the other side of the discharge space P (lower side in FIG. 2). As described above, the reaction gas supply port 41 and the vacuum pump 81 are arranged to face each other via the discharge space P, so that the reaction gas can be efficiently supplied to the discharge space P, and plasma is more easily generated. can do.

  As the reaction gas supplied to the discharge space P, a gas that contains at least oxygen gas and reacts with the raw material gas to become an inorganic compound such as oxide or nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  In the present embodiment, the source gas supply port 31 and the reaction gas supply port 41 are individually provided. However, in a state where the source gas and the reaction gas are mixed in advance, the one supply port enters the discharge space P. The structure supplied may be sufficient. Further, in order to supply the source gas or the reaction gas into the vacuum chamber 80, a carrier gas may be used as necessary. Further, in order to generate plasma discharge, a discharge gas may be used as necessary. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon and xenon; hydrogen; nitrogen can be used.

  As a ratio of the source gas and the reactive gas, it is preferable that the ratio of the reactive gas is not excessively larger than a ratio of the amount of the reactive gas that is theoretically necessary for completely reacting the raw material gas and the reactive gas. By not excessively increasing the ratio of the reaction gas, the barrier film 3 formed is excellent in that excellent barrier properties and bending resistance can be obtained. In the case of containing an organic silicon compound as a raw material gas and oxygen as a reaction gas, the amount is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organic silicon compound.

  A vacuum pump 81 is connected to the vacuum chamber 80, and the pressure in the vacuum chamber 80 can be appropriately adjusted by the vacuum pump 81.

  The adjusting means 50 adjusts the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P when forming the barrier film 3 to be 0.05 or more and 1.0 or less. As shown in FIG. 2, the adjusting unit 50 includes a drying unit 51 and a reducing unit 52. In FIG. 2, the reducing means 52 is shown in a front sectional view for easy understanding.

  The drying means 51 dries moisture contained in the substrate 2 outside the vacuum chamber 80. The drying means 51 is, for example, a heater, but is not particularly limited as long as it is configured to dry moisture contained in the substrate 2. Since the adjusting unit 50 includes the drying unit 51, the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas can be easily adjusted.

  The reducing unit 52 reduces the water vapor gas in the discharge space P by cooling and condensing the water in the vacuum chamber 80. The reducing means 52 is a cooling coil arranged in a coil shape over the entire area in the vacuum chamber 80. The reducing means 52 cools the inside of the vacuum chamber 80 by the refrigerant flowing through the inner cavity 52a. The reducing means 52 is not limited to the cooling coil as long as it is configured to reduce the water vapor gas in the discharge space P by cooling and condensing the moisture in the vacuum chamber 80. Since the adjusting unit 50 includes the reducing unit 52, the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas can be easily adjusted.

  Thus, the adjusting means 50 adjusts the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P when forming the barrier film 3 to be 0.05 or more and 1.0 or less. be able to. Hereinafter, the effect of forming the barrier film 3 in the discharge space P in which the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas is 0.05 to 1.0 will be described.

As described above, the barrier properties of the gas barrier film have not been sufficient in the prior art. In particular, in the film containing ₃ to 33% of the carbon component, it has been found by the present inventors that many CH ₃ groups remain in the film, and as a result, minute voids are formed around the CH ₃ group. As a result, it was found that when exposed to a high-temperature and high-humidity environment, there is a problem that the molecular structure bonds in the pores are broken and cracks occur.

  Therefore, the present inventors paid attention to water molecules as a means for suppressing fine pores in the barrier film. As a result of investigation, in water deposition by plasma CVD, when water molecules are exposed to plasma, OH groups having higher activity than oxygen are generated, and when they react with raw material molecules, precursor molecules containing OH groups are formed. I understood that. The formed precursor molecules react with unreacted groups present in the vacancies of the barrier film, thereby filling the vacancies with the precursor and reducing the gap. It was found that blocking the air holes eliminates the passage of water molecules and provides a sufficient barrier property. Furthermore, since the void | hole was block | closed, it turned out that the coupling | bonding of the molecular structure of a void | hole part is hard to be cut | disconnected, and generation | occurrence | production of a crack is suppressed. For this reason, it is preferable that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P is 0.05 or more.

As a result of various investigations on the method for closing the vacancies as described above, the ratio (H ₂ O / O ₂ ) of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas during film formation in the plasma CVD method is 0.05 or more. When it was 1.0 or less, it was found that a barrier film having small pores was formed, and a barrier film having sufficient barrier properties was obtained.

  By adjusting the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas to 0.05 or more and 1.0 or less by the adjusting means 50 described above, the barrier film 3 having small pores is formed and sufficient barrier properties are obtained. The barrier film is obtained. Further, the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas is more preferably 0.1 or more and 0.8 or less because the effect of improving the barrier property is higher.

  The measuring means 60 measures the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas in the discharge space P. The measuring means 60 is a mass analyzer. Specifically, the mixed gas containing the oxygen gas and the water vapor gas in the discharge space P is measured by the measuring means 60 attached to the wall surface of the vacuum chamber 80, and the water vapor corresponding to the partial pressure of the oxygen gas in the mixed gas is measured. Measure the gas partial pressure ratio. Further, based on the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P measured by the measuring means 60, the adjusting means 50 determines the distribution of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P. It is preferable to adjust the pressure ratio.

  Next, the manufacturing method of the gas barrier film 1 which concerns on 1st Embodiment is demonstrated.

  The manufacturing method of the gas barrier film 1 according to the present embodiment can be summarized as a first film formation in which the base material 2 is stretched while supplying a source gas containing carbon and a reaction gas containing oxygen gas into the vacuum chamber 80. With respect to the roll 19 and the second film-forming roll 20 that stretches the substrate 2 that is disposed to face the first film-forming roll 19 with a predetermined distance apart and passes through the first film-forming roll 19. This is a method for producing the gas barrier film 1 by plasma CVD, in which a high-frequency voltage is applied to form a barrier film 3 on the surface of the substrate 2 in the discharge space P. The manufacturing method of the gas barrier film 1 is adjusted so that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P when forming the barrier film 3 is 0.05 or more and 1.0 or less. It has an adjustment process. Hereinafter, the manufacturing method of the gas barrier film 1 which concerns on this embodiment is explained in full detail.

  First, a predetermined amount of moisture contained in the substrate 2 is dried outside the vacuum chamber 80 by the drying means 51 (adjustment process). Specifically, when the barrier film 3 is formed, the base material 2 is set so that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas is 0.05 or more and 1.0 or less in the discharge space P. The moisture contained in is dried.

  Next, the base material 2 dried by the drying means 51 is set in the vacuum chamber 80, and the raw material is supplied into the vacuum chamber 80 through the raw material gas supply port 31 while the pressure in the vacuum chamber 80 is reduced by the vacuum pump 81. A gas is supplied, and a reactive gas is supplied through the reactive gas supply port 41. Thereby, the source gas and the reaction gas can be filled in the discharge space P of the vacuum chamber 80.

  At this time, the moisture in the vacuum chamber 80 is cooled and condensed by the reducing means 52, thereby reducing the water vapor gas in the discharge space P (adjustment process). Specifically, in the discharge space P, the water vapor gas in the discharge space P is reduced so that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas is 0.05 or more and 1.0 or less.

  Next, while supplying the source gas and the reaction gas into the vacuum chamber 80, a discharge is generated by the plasma generating power source 22 in the discharge space P between the first film forming roll 19 and the second film forming roll 20. Thus, the source gas and the reactive gas are decomposed and reacted in the plasma, and the barrier film is formed on the surface of the base material 2 on the first film forming roll 19 and the surface of the base material 2 on the second film forming roll 20. 3 is formed by plasma CVD.

  Further, the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P is measured by the measuring means 60 (measuring process), and the adjusting means 50 is based on the numerical value of the ratio measured by the measuring means 60. The ratio is adjusted (adjustment process). According to this process, the ratio in the discharge space P can be adjusted more accurately.

  The partial pressure of the oxygen gas in the vacuum chamber 80 when the barrier film 3 is formed can be adjusted as appropriate according to the type of the raw material gas, but from the viewpoint of further improving the barrier property. It is preferable to set it in the range of 05 Pa or more and 2.0 Pa or less. The oxygen gas partial pressure is preferably 0.05 Pa or more and 1.0 Pa or less. The oxygen gas partial pressure is more preferably 0.10 Pa or more and 1.0 Pa or less.

  Moreover, it is preferable that the total pressure in the vacuum chamber 80 when forming the barrier film 3 is 1.0 Pa or more and 5.0 Pa or less from the viewpoint of further improving the barrier property.

  Although the conveyance speed of the base material 2 can be suitably adjusted according to the kind of source gas, the pressure in the vacuum chamber 80, etc., it is preferable to set it as the range of 5-80 m / min. If it is this range, since a conveyance speed is quick, it is hard to receive a heat damage, and also productivity improves. In addition, since the water | moisture content in the vacuum chamber 80 increases with the increase in the water | moisture content contained in the base material 2 so that conveyance speed is fast, more water | moisture content contained in the base material 2 is dried by the drying means 51. Alternatively, it is necessary to reduce the water vapor gas in the discharge space P more by the reducing means 52. It is preferable that a conveyance speed is 10-50 m / min from a viewpoint of improving barrier property more. The conveyance speed is more preferably 10 to 40 m / min.

  As described above, in the method for manufacturing the gas barrier film 1 according to this embodiment, the first material for stretching the substrate 2 while supplying the source gas containing carbon and the reaction gas containing oxygen gas into the vacuum chamber 80 is provided. Production of a gas barrier film by plasma CVD, in which a high-frequency voltage is applied to the film-forming roll 19 and the second film-forming roll 20 to form a barrier film 3 on the surface of the substrate 2 in the discharge space P Is the method. The gas barrier film manufacturing method is adjusted so that the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas in the discharge space P is 0.05 or more and 1.0 or less when the barrier film 3 is formed. Process. According to this manufacturing method, the gas barrier film 1 that can further improve the barrier properties can be manufactured.

  In addition, as described above, the gas barrier film 1 manufacturing apparatus 100 according to the present embodiment stretches the base material 2 while supplying the source gas containing carbon and the reaction gas containing oxygen gas into the vacuum chamber 80. A gas barrier by plasma CVD, in which a high-frequency voltage is applied to the first film forming roll 19 and the second film forming roll 20 to form a barrier film 3 on the surface of the substrate 2 in the discharge space P. This is a film manufacturing apparatus 100. The apparatus 100 for producing the gas barrier film 1 is adjusted so that the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas in the discharge space P when the barrier film 3 is formed is 0.05 to 1.0. And adjusting means 50 for adjusting. According to this manufacturing apparatus, the gas barrier film 1 that can further improve the barrier property can be manufactured.

Second Embodiment
Next, the manufacturing apparatus 200 of the gas barrier film 1 which concerns on 2nd Embodiment of this invention is demonstrated. Description of parts common to the first embodiment will be omitted, and only features unique to the second embodiment will be described. The gas barrier film 1 manufacturing apparatus 200 according to the second embodiment is different from the gas barrier film 1 manufacturing apparatus 100 according to the first embodiment in the configuration of the adjusting means 150.

  FIG. 3 is a view showing an apparatus 200 for manufacturing the gas barrier film 1 according to the second embodiment.

  The apparatus 200 for producing the gas barrier film 1 according to the second embodiment includes a delivery roll 14, transport rolls 15, 16, 17, 18, a take-up roll 25, film forming rolls 19, 20, and a plasma generation power source 22. Magnetic field generators 23, 24, source gas supply port 31, source gas supply unit 32, reaction gas supply port 41, reaction gas supply unit 42, water vapor gas supply unit 160, vacuum chamber 80, The vacuum pump 81, the adjusting unit 150, and the measuring unit 60 are included. Delivery roll 14, transport rolls 15, 16, 17, 18, take-up roll 25, film forming rolls 19, 20, plasma generation power source 22, magnetic field generators 23, 24, source gas supply port 31, source gas supply unit 32 Since the reaction gas supply port 41, the reaction gas supply unit 42, the vacuum chamber 80, the vacuum pump 81, and the measuring unit 60 have the same configuration as the gas barrier film 1 manufacturing apparatus 100 according to the first embodiment, the description thereof is omitted. To do.

  The water vapor gas supply unit 160 is disposed outside the vacuum chamber 80. The water vapor gas stored in the water vapor gas supply unit 160 is supplied into the discharge space P through the reaction gas supply port 41. The water vapor gas stored in the water vapor gas supply unit 160 is supplied into the discharge space P by a vaporizer or a bubbler.

  The adjusting unit 150 includes an adjusting valve 151 that adjusts the flow rate of the water vapor gas supplied into the vacuum chamber 80 and an adjusting valve 152 that adjusts the flow rate of the reaction gas containing oxygen gas. In the second embodiment, the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas in the discharge space P when the barrier film 3 is formed by the regulating valves 151 and 152 is 0.05 or more and 1.0 or less. It is adjusted to become.

  Next, the manufacturing method of the gas barrier film 1 which concerns on 2nd Embodiment is demonstrated. Since the manufacturing method according to the second embodiment differs from the manufacturing method according to the first embodiment only in the adjustment process, only the adjustment process will be described.

  In the adjustment process, while adjusting the water vapor gas and the oxygen gas supplied to the discharge space P by the adjustment valves 151 and 152, while supplying the reaction gas containing the water vapor gas and the oxygen gas to the discharge space P (supply process), Supply raw material gas. Specifically, in the discharge space P, the ratio of the partial pressure of the water vapor gas to the partial pressure of the oxygen gas when forming the barrier film 3 is adjusted to be 0.05 or more and 1.0 or less.

  As explained above, according to the manufacturing method and manufacturing apparatus 200 of the gas barrier film 1 which concerns on 2nd Embodiment, a ratio can be adjusted more easily.

  The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims.

  For example, in the first embodiment described above, the adjustment unit 50 includes the drying unit 51 and the reduction unit 52. However, a configuration including either the drying unit 51 or the reduction unit 52 is also included in the present invention.

  In the first embodiment described above, the adjustment unit 50 includes the drying unit 51 and the reduction unit 52. However, the adjustment unit 50 may further include the adjustment valves 151 and 152 according to the second embodiment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<Example 1>
[Production of gas barrier film]
(Preparation of base material)
A 50 μm thick polyethylene terephthalate (PET) film (manufactured by Teijin DuPont Films, trade name “Teijin Tetron Film”) was used as a substrate.

(Formation of anchor layer)
Using the UV curable organic / inorganic hybrid hard coat material OPSTARZ7501 manufactured by JSR Corporation on the easy-adhesion surface side of the substrate, and applying with a wire bar so that the layer thickness after drying is 4 μm, And drying at 80 ° C. for 3 minutes. Next, curing was carried out under an air atmosphere using a high-pressure mercury lamp under curing conditions; 1.0 J / cm ² to form an anchor layer.

(Formation of barrier film)
Using the plasma CVD apparatus shown in FIG. 3, the base material is mounted on the apparatus so that the side opposite to the anchor layer (back surface) of the base material is in contact with the film forming roller. According to (Condition), a barrier film was formed on the anchor layer under the condition that the thickness was 100 nm. Water was supplied using a vaporizer and the flow rate was adjusted so that the water vapor gas had a predetermined partial pressure. The partial pressure of oxygen gas and water vapor gas is measured by a mass analyzer, and the ratio of the partial pressure of water vapor gas to the partial pressure of oxygen gas is set to a predetermined ratio based on the measured value. The flow rate of was adjusted.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisiloxane, abbreviation: HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Resin substrate transport speed: 10 m / min
Table 1 below shows the total pressure, the partial pressure of oxygen gas, the partial pressure of water vapor gas, the partial pressure ratio of water vapor gas to oxygen gas, and the conveyance speed.

<Examples 2 to 16>
In Examples 2 to 16, barrier films were produced in the same manner as in Example 1 except that the film formation conditions shown in Table 1 below were used.

<Example 17>
In Example 1, a barrier film was produced in the same manner as in Example 1 except that the source gas was changed from HMDSO to tetraisopropyl titanate.

<Example 18>
In Example 1, a barrier film was produced in the same manner as in Example 1 except that the source gas was changed from HMDSO to aluminum sec-butyrate.

<Comparative Examples 1-2>
In Comparative Examples 1 and 2, barrier films were produced in the same manner as in Example 1 except that the film formation conditions shown in Table 1 below were used.

<Evaluation method>
The obtained gas barrier film was allowed to stand for 48 hours in a high-temperature and high-humidity tank at 85 ° C. and 85% RH. Before and after that, the following barrier properties were evaluated. Moreover, the following cracks were evaluated for occurrence of cracks after standing under high temperature and high humidity.

(Evaluation of water vapor barrier properties)
According to the following measuring method, the water vapor barrier property of each gas barrier film was evaluated.

・ Equipment Vapor deposition device: JE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
-Manufacture of the cell for water vapor | steam barrier property evaluation The metal calcium was vapor-deposited on the surface of the gas barrier film using the vacuum evaporation apparatus (JEOL vacuum evaporation apparatus JEE-400). After that, in a dry nitrogen gas atmosphere, the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays. An evaluation cell was produced.

  The obtained sample (evaluation cell) was stored under high temperature and high humidity of 85 ° C. and 85% RH, and the time taken for the metal calcium to corrode 100% was measured.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, instead of the gas barrier film as a comparative sample, a sample in which metallic calcium was deposited using a quartz glass plate having a thickness of 0.2 mm, The same storage at 85 ° C. and 85% RH under high temperature and high humidity was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

  The 100% corrosion time of each gas barrier film thus obtained was determined before and after standing in a high temperature and high humidity environment. The evaluation criteria were as follows.

○: Gas barrier property change rate is in the range of 10% or less. Δ: Gas barrier property change rate is in the range of more than 10% to 50% or less. X: Gas barrier property change rate is more than 50%. Evaluation of)
The obtained sample (evaluation cell) was stored at 85 ° C. and 85% RH under high temperature and high humidity for 2 hours, and the number of places where the metallic calcium was discolored and the diameter was 300 μm or more was counted as the number of cracks. The evaluation criteria were as follows.

○: Number of cracks is less than 1 / cm ² Δ: Number of cracks is 1 / cm ² or more and less than 10 / cm ² ×: Number of cracks is 10 / cm ² or more

  As can be seen from Table 1, Examples 1 to 18 were compared with Comparative Examples 1 and 2 by controlling the partial pressure ratio of oxygen and moisture during film formation to a range of 0.05 to 1.0. Excellent barrier properties and cracking suppression effect were shown.

  Furthermore, the present application is based on Japanese Patent Application No. 2015-010662 filed on January 22, 2015, the disclosures of which are incorporated by reference in their entirety.

1 gas barrier film,
2 base material,
3 barrier film,
19 First film forming roll,
20 Second film forming roll,
50,150 adjustment means,
51 drying means,
52 reduction means,
60 measuring means,
151,152 regulating valve,
160 water vapor gas supply unit,
80 vacuum chamber,
P discharge space.

Claims (14)

While supplying at least a source gas containing carbon and a reaction gas containing oxygen gas into the vacuum chamber, the first film forming roll that stretches the substrate and the first film forming roll are separated from each other by a predetermined distance. Then, a high-frequency voltage is applied to the second film-forming roll that stretches the base material that is disposed opposite to and passes through the first film-forming roll, and the first film-forming roll and the second film-forming roll A method for producing a gas barrier film by plasma CVD, wherein a barrier film is formed on the surface of the substrate in a discharge space formed between film forming rolls,
A gas barrier film having an adjustment step of adjusting a ratio of a partial pressure of water vapor gas to a partial pressure of oxygen gas in the discharge space to be 0.05 or more and 1.0 or less when forming the barrier film Production method.   The method for producing a gas barrier film according to claim 1, wherein in the adjustment step, the ratio is adjusted by drying moisture contained in the base material outside the vacuum chamber.   The gas barrier film according to claim 1 or 2, wherein, in the adjustment step, the ratio is adjusted by reducing the water vapor gas in the discharge space by cooling and condensing moisture in the vacuum chamber. Method. A supply step of supplying the water vapor gas into the vacuum chamber;
The gas barrier film according to any one of claims 1 to 3, wherein in the adjustment step, the ratio is adjusted by adjusting a flow rate of the water vapor gas and / or the oxygen gas supplied into the vacuum chamber. Production method.   The manufacturing method of the gas barrier film of any one of Claims 1-4 adjusted so that the said ratio may be 0.1 or more and 0.8 or less in the said adjustment process.   The method for producing a gas barrier film according to any one of claims 1 to 5, wherein a partial pressure of the oxygen gas in the vacuum chamber when forming the barrier film is 0.05 Pa or more and 1.0 Pa or less. .   The method for producing a gas barrier film according to claim 1, wherein a total pressure in the vacuum chamber when forming the barrier film is 1.0 Pa or more and 5.0 Pa or less.   The method for producing a gas barrier film according to any one of claims 1 to 7, wherein a conveying speed for feeding the substrate is 5 to 80 m / min. Further comprising a measuring step of measuring the ratio in the discharge space;
The manufacturing method of the gas barrier film of any one of Claims 1-8 which adjusts the said ratio in the said adjustment process based on the numerical value of the said ratio measured in the said measurement process. While supplying at least a source gas containing carbon and a reaction gas containing oxygen gas into the vacuum chamber, the first film forming roll that stretches the substrate and the first film forming roll are separated from each other by a predetermined distance. Then, a high-frequency voltage is applied to the second film-forming roll that stretches the base material that is disposed opposite to and passes through the first film-forming roll, and the first film-forming roll and the second film-forming roll An apparatus for producing a gas barrier film by plasma CVD, which forms a barrier film on the surface of the substrate in a discharge space formed between film forming rolls,
A gas barrier film having adjusting means for adjusting a ratio of a partial pressure of water vapor gas to a partial pressure of oxygen gas in the discharge space to be 0.05 or more and 1.0 or less when forming the barrier film manufacturing device.   The said adjustment means is a manufacturing apparatus of the gas barrier film of Claim 10 which has a drying means to dry the water | moisture content contained in the said base | substrate outside the said vacuum chamber.   The apparatus for producing a gas barrier film according to claim 10 or 11, wherein the adjusting means includes a reducing means for reducing the water vapor gas in the discharge space by cooling and condensing moisture in the vacuum chamber. A water vapor gas supply unit for supplying water vapor gas into the vacuum chamber;
The apparatus for producing a gas barrier film according to any one of claims 10 to 12, wherein the adjusting means includes an adjusting valve that adjusts a flow rate of the water vapor gas and / or the oxygen gas supplied into the vacuum chamber. Further comprising measuring means for measuring the ratio in the discharge space;
The apparatus for producing a gas barrier film according to any one of claims 10 to 13, wherein the ratio is adjusted by the adjusting means based on the numerical value of the ratio measured by the measuring means.