JP2011036778A - Method for producing barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a barrier film having an inorganic barrier layer and a polymer layer on a base material film, the barrier film having stable and high gas barrier properties. <P>SOLUTION: In the method for producing the barrier film having at least one inorganic barrier layer and at least one polymer layer on the base material film, when a coating liquid for forming the polymer layer is applied, by an application method, to the surface of the inorganic barrier layer to form the polymer layer on the inorganic barrier layer, the coating liquid for forming the polymer layer is degassed and is then applied at a temperature which is lower by 20-60°C than the boiling point of a solvent composing the coating liquid for forming the polymer layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a barrier film having excellent gas barrier performance. More specifically, the present invention relates to a method for producing a barrier film having extremely excellent gas barrier performance suitable for or as a substrate for foods, pharmaceuticals and various devices.

In recent years, in the packaging field of foods, pharmaceuticals, industrial products, and the like, gas barrier films against the permeation of oxygen and water vapor have been used as packaging materials in order to prevent alteration of the packaged contents. Conventionally, as a gas barrier film, for example, a film coated with a gas barrier resin such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), or polyvinylidene chloride (PVDC), or a film made of these resins. A laminated film in which a thin film of a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or film has been used. All of these laminate films are known to have a water vapor barrier property of about 1 g / m ² · day.

  These gas barrier films have recently been used in substrates and packaging materials such as liquid crystal display elements, solar cells, and organic EL elements in addition to food and pharmaceutical packaging materials.

  In particular, image display elements such as liquid crystal display elements and organic EL elements in recent years have been studied for roll-to-roll systems that are highly productive in addition to being lighter, larger, and used as transparent plastic substrates and sealing materials from glass substrates. It is supposed to be done.

  However, as a drawback of the transparent plastic substrate, there is a gas barrier property as compared with the glass substrate. Moreover, it cannot be said that the gas barrier property as a sealing material is sufficient.

  In the case of an image display element such as a liquid crystal display element or an organic EL element, if a base material and a sealing material with inferior gas barrier properties are used, water vapor or air permeates, for example, deteriorates the liquid crystal in the liquid crystal cell, resulting in a display defect. Display quality.

Furthermore, in a large-sized liquid crystal display, a high-definition display, and the like that have been developed in recent years, a water vapor transmission rate of 0.1 g / m ² · day to 0.01 g / m ² · day is required.

  In order to cope with such a problem, a barrier film in which a metal oxide thin film such as silicon oxide or aluminum oxide is formed on a transparent plastic substrate has been developed so far. For example, Japanese Patent Application Laid-Open No. 2003-045653 discloses a film in which ceramic is deposited on the side where a transparent electrode is not formed using polyethylene terephthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, or the like. Are known.

  As a problem of the barrier film in which such a metal oxide thin film is formed, there is a gas barrier defect due to cracking of the metal oxide thin film. So far, this metal oxide thin film has been studied for cracking. For example, a laminate in which an aluminum oxide vapor-deposited thin film layer, a gas barrier film layer containing a water-soluble polymer, and an aluminum oxide vapor-deposited thin film layer are sequentially laminated on at least one surface of a transparent substrate film made of a polymer material is known. (See Patent Document 1).

  There is known a barrier film having a barrier layer and an organic layer containing an inorganic substance alternately on a support at least one layer at a time (see Patent Document 2).

  A barrier film having at least one inorganic barrier layer and at least one organic layer mainly composed of a polymer of an acrylic monomer on a base film is known (see Patent Document 3).

  However, the barrier films described in Patent Documents 1 to 3 have improved gas barrier properties against oxygen and water vapor permeation as compared with barrier films in which a metal oxide thin film is formed on a base film, but still have high gas barrier properties. It was found to be insufficient for use in required image display elements such as liquid crystal display elements and organic EL elements.

  Under such circumstances, it is desired to develop a barrier film having a stable and high gas barrier property, which is a laminated film having an inorganic barrier layer having a metal oxide and a polymer layer on a base film.

JP 2003-181973 A JP 2006-088538 A JP 2008-87162 A

  The present invention has been made in view of such circumstances, and the object thereof is a barrier film having an inorganic barrier layer and a polymer layer on a base film, and provides a method for producing a stable barrier film having a high gas barrier property. It is to be.

  The above object of the present invention has been achieved by the following constitution.

1. In the method for producing a barrier film having at least one inorganic barrier layer and at least one polymer layer on the film substrate,
When applying and forming a polymer layer forming coating solution on the inorganic barrier layer by a coating method,
After degassing the polymer layer forming coating solution, the barrier layer is applied at a temperature lower by 20 to 60 ° C. than the boiling point of the solvent constituting the polymer layer forming coating solution. Production method.

  2. 2. The method for producing a barrier film as described in 1 above, wherein a deaeration degree of the coating liquid for forming a polymer layer is 30% or less.

  3. 3. The method for producing a barrier film as described in 1 or 2 above, wherein the polymer layer is formed of an acrylate resin or a methacrylate resin.

  4). 3. The method for producing a barrier film as described in 1 or 2 above, wherein the polymer layer is made of polysilazane.

  5. 5. The method for producing a barrier film according to any one of 1 to 4, wherein the polymer layer includes particles having an average particle diameter of 7 nm to 100 nm.

  6). 6. The method for producing a barrier film according to any one of 1 to 5, wherein the inorganic barrier layer is a silicon oxide-based barrier film formed by an atmospheric pressure plasma method.

  As a result of examining why the inorganic barrier layer and the polymer layer are alternately laminated on the base material and why the oxygen transmission rate and the water vapor transmission rate are not stable, the present inventor has found the following.

  In the laminated film with the inorganic barrier layer and the polymer layer alternately on the film substrate, the stability of the inorganic barrier layer is dominant for maintaining the performance of the gas barrier property. It was estimated that gas barrier properties could be stabilized.

  The gas barrier property of the inorganic barrier layer formed on the base material is unstable. This is because the inorganic barrier layer is thin and hard, and fine cracks and defects due to the removal of fine foreign substances are generated during the manufacturing process. Even if the polymer layer is applied on the inorganic barrier layer, the coating liquid for forming the polymer layer enters inside the crack and inside the defect and does not seal the crack and the defective part. Presumed to be due to entering.

  The reason why the coating liquid for forming the polymer layer does not enter the crack and the defect portion is that the crack and the defect portion are fine, so the air inside the crack and the defect when the coating solution for forming the polymer layer is applied. Is in a state of being contained by the coating solution for forming the polymer layer. As a result, it has been found that the gas barrier properties are destabilized when water vapor and oxygen that have passed through the polymer layer formed by the polymer layer forming coating liquid enter through the cracks and the defective portions.

  Furthermore, as a means of preventing the occurrence of cracks in the inorganic barrier layer formed on the film substrate, the method of forming the inorganic barrier layer was examined, and as a result, the atmospheric pressure plasma method was better than the vapor phase volume method by vacuum deposition. Although it was excellent, it was found that since the base material is a flexible film, the inorganic barrier layer cannot follow the flexibility of the base material and cracks are generated.

  From these facts, it is quite difficult to prevent the occurrence of cracks when using a flexible film as a base material, so when applying the polymer layer forming coating liquid to the air inside the cracks and inside the defects. As a result of finding out that the intended effect of the present invention can be achieved by removing, and further, by including particles in the polymer layer, the effect of shielding the inside of the crack and the inside of the defect can be obtained. It is.

  It was possible to provide a barrier film having a stable and high gas barrier property with a laminated film having an inorganic barrier layer having at least one metal oxide layer and a polymer layer on a base film.

It is a general | schematic expanded sectional view of a barrier film. It is a schematic diagram of the manufacturing process of a barrier film. It is the schematic which showed an example of the jet type atmospheric pressure plasma film-forming apparatus. It is the schematic which shows an example of the atmospheric pressure plasma film-forming apparatus of the system which processes a base material between counter electrodes.

  Hereinafter, modes for carrying out the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to these.

  FIG. 1 is a schematic enlarged cross-sectional view of a barrier film.

  In the figure, 1 is a barrier film. 101 shows a base material. Reference numeral 102 denotes an inorganic barrier layer having a gas barrier property formed on the substrate 101. Reference numeral 103 denotes a polymer layer formed on the inorganic barrier layer 102.

The barrier film 1 shown in the figure shows a case where the inorganic barrier layer 102 and the polymer layer 103 are each one layer, but are not limited thereto. Further, a polymer layer or an adhesion layer may be provided between the substrate and the inorganic barrier layer. The inorganic barrier layer portion may have a laminated structure of two or more layers having different compositions or physical properties. Other configurations include the following configurations. For example,
1) Substrate / Inorganic barrier layer / Polymer layer / Inorganic barrier layer / Polymer layer / Inorganic barrier layer,
2) substrate / inorganic barrier layer / polymer layer / inorganic barrier layer,
3) Substrate / Inorganic barrier layer / Inorganic barrier layer / Polymer layer / Inorganic barrier layer,
4) Substrate / Inorganic barrier layer / Polymer layer / Polymer layer / Inorganic barrier layer The barrier film having these layer structures can be selected as necessary.

  The inorganic barrier layer 102 is a layer having an effect of blocking gas such as water vapor and oxygen, and is formed of a thin film mainly composed of a ceramic component such as a metal oxide, a metal nitride oxide, or a metal nitride. The average carbon content is preferably less than 1%.

  The thickness of the substrate 101 is preferably 12 μm to 500 μm in consideration of flexibility, transportability, and the like.

  The substrate 101 is preferably a resin film having transparency with an average transmittance in the visible light region of 85% or more. The average transmittance in the visible light region referred to in the present invention is obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 nm to 700 nm at least every 5 nm, and calculating an average value thereof. Defined as For the transmittance at each measurement wavelength, a conventionally known measuring device can be used. For example, a spectrophotometer UVIDFC-610 manufactured by Shimadzu Corporation, a 330-type self-recording spectrophotometer manufactured by Hitachi, Ltd., a U-3210-type self-recording It can obtain | require by measuring using a spectrophotometer, a U-3410 type self-recording spectrophotometer, a U-4000 type self-recording spectrophotometer, etc.

  The thickness of the inorganic barrier layer 102 is preferably 10 nm to 1000 nm in consideration of gas barrier properties, crack resistance, storage stability, and the like. More preferably, it is 10 nm to 200 nm. When the inorganic barrier layer is composed of a plurality of inorganic barrier layers, the total thickness of the inorganic barrier layers is preferably within the above range. The inorganic barrier layer may have two or more inorganic barrier layers, and in that case, each layer may have the same composition or different compositions.

  The formation of the inorganic barrier layer 102 is not particularly limited, and examples thereof include a sputtering method, a vacuum evaporation method, an ion plating method, and a plasma CVD method. Among these, it is preferable to be formed by applying a plasma CVD method or the like under atmospheric pressure or a pressure near atmospheric pressure. In particular, the method using atmospheric pressure plasma CVD does not require a decompression chamber or the like, and is manufactured at high speed. This is a film forming method with high productivity. A specific method of forming the inorganic barrier layer will be described with reference to FIGS.

  The thickness of the polymer layer 103 is preferably 10 nm to 5000 nm, more preferably 50 nm to 4000 nm in consideration of uniformity of the thickness of the polymer layer, crack resistance of the polymer layer, sealing of cracks in the inorganic barrier layer, and the like. Most preferably, it is 50 nm to 3000 nm. When there are a plurality of polymer layers, the total thickness of the polymer layers is preferably within the above range.

  The polymer layer of the present invention preferably contains particles having an average particle diameter of 7 nm to 100 nm. By having particles in the polymer layer, when the degassed coating liquid of the present invention penetrates into cracks and / or defects in the barrier layer, the inside is filled with particles, so that an oxygen / water vapor blocking effect is obtained. It gets even higher. The material of the particle is not particularly limited, but an inorganic metal compound particle selected from Al, Si, Ti, Zr and the like is preferable. Alkaline earth metal compounds such as BaO and CaO are also preferable. Considering coating liquid dispersibility, cracks, penetration into defects, and the like, it is preferable that particles having an average particle diameter of 7 nm to 100 nm are included. More preferably, it is 7 nm to 50 nm, and most preferably 7 nm to 20 nm.

  The coating method of the coating liquid for forming the polymer layer 103 for forming the polymer layer 103 is not particularly limited. For example, spin coating coating, dip coating, extrusion coating, roll coating coating, spray coating, gravure coating, wire bar coating, air knife Application etc. are mentioned. It is possible to select from these application methods as required.

  FIG. 2 is a schematic view of the polymer film manufacturing process of the barrier film.

  In the figure, reference numeral 2 denotes a barrier film manufacturing process. The production process 2 includes a base material supply process 3, a polymer layer forming coating solution supply process 4, a coating process 5, a drying process 6, and a winding process 7.

  From the base material supplying step 3, the long base material 301 having an inorganic barrier layer already formed and wound in a roll shape is fed out from the unwinding roll by a driving means (not shown) and conveyed (in the direction of the arrow in the figure). Is done.

  The polymer layer forming coating solution supply step 4 uses a polymer layer forming coating solution storage tank 401, a deaeration device 402, and a heating device 403. The polymer layer forming coating solution storage tank 401 is preferably provided with a temperature control system for controlling the temperature of the polymer layer forming coating solution when deaeration is performed by the deaerator 402.

  The temperature of the polymer layer forming coating solution in the polymer layer forming coating solution storage tank 401 is based on the boiling point of the solvent constituting the polymer layer forming coating solution in consideration of dispersibility of the coating solution, degassing efficiency, and the like. It is preferably 20 to 100 ° C. lower.

  The polymer layer forming coating solution used in the present invention may be either an aqueous solution or an organic solvent, but an organic solvent is preferred.

  The degassing device 402 is a device for degassing the polymer layer forming coating solution sent from the polymer layer forming coating solution storage tank 401 via the liquid feeding tube 401a. The deaeration device 402 is not particularly limited. For example, as described in an ultrasonic deaeration device, a heating deaeration device, a vacuum deaeration device, and Japanese Patent Application Laid-Open No. 11-209670, a deaeration method using a deaeration hollow fiber membrane. And a gas-liquid separation membrane module described in JP-A No. 2004-181403, and the like can be selected as necessary.

  The degree of deaeration of the coating solution for forming a polymer layer deaerated by the deaerator 402 is preferably 30% or less, and the lower limit is preferably 10% in consideration of barrier properties, productivity, and the like.

  Regarding the degree of deaeration, the amount of saturated dissolved oxygen at the deaeration temperature and the amount of dissolved oxygen after deaeration are measured according to the following procedure for the polymer layer forming coating solution, and the amount of dissolved oxygen after saturation / saturated dissolved. The ratio of the amount of oxygen was determined, and the ratio of the dissolved air amount in the polymer layer forming coating solution to the saturated air dissolved amount, that is, the degree of deaeration.

  Examples of the method for measuring the dissolved oxygen concentration include the Ostwald method (see Experimental Chemistry Course 1, Basic Operation [I], page 241, 1975, Maruzen), the method of measuring by the mass spectrum method, the galvanic cell type, and the polarographic type. It can be measured using a simple oxygen concentration meter such as a colorimetric method. The dissolved oxygen concentration can also be easily measured using a commercially available dissolved oxygen concentration meter (DO-30A type manufactured by Toa Denpa Kogyo Co., Ltd.).

  The heating device 403 is a device that heats the polymer layer forming coating liquid deaerated by the deaeration device 402 to a temperature at which it is applied, and there is no particular limitation on the heating method. The method of heating with a heater is mentioned. Organic solvents generally have a higher saturation solubility of gases and higher gas dissolution rates than aqueous solutions. Furthermore, many organic solvents tend to increase in solubility with increasing temperature. From this, by heating, the dissolution rate of the gas of the coating liquid for forming a polymer layer using an organic solvent can be increased, and the solubility can be increased.

  The coating process 5 uses a coater 501 and a backup roll 502 that winds and holds the substrate 301. In addition, it is preferable that the coater 501 is provided with temperature control means (attached illustration) in order to maintain the temperature of the polymer layer forming coating solution heated by the heating device 403. This figure shows the case of an extrusion coating type extrusion coater as the coater.

  The temperature of the coating liquid for forming a polymer layer at the time of coating is 20 to 60 ° C. lower than the boiling point of the solvent constituting the coating liquid for forming a polymer layer. When the temperature is lower than 20 ° C., the concentration of the coating liquid for forming the polymer layer and the increase in viscosity are increased due to the evaporation of the organic solvent in the coating liquid for forming the polymer layer, which makes it difficult to apply a stable film thickness. When the temperature exceeds 60 ° C., the dissolution rate of dissolving the air present in the cracks and defects of the inorganic barrier layer into the coating liquid for forming the polymer layer is slow, and the gas barrier property becomes unstable, which is not preferable.

  The drying step 6 is a step of removing the organic solvent from the wet film of the coating liquid for forming the polymer layer applied on the inorganic barrier layer in the applying step 5 to form a polymer layer. Yes.

In the drying step 6, the residual solvent amount of the coating film is, barrier property, considering productivity and the like, it is preferable to dry the 100 g / ^{m 2} as a 10 g / ^{m 2.} The residual solvent amount of the coating film was measured by the following method.

The amount of the residual solvent was measured by cutting the base material on which the polymer layer was formed into a 10 cm square, measuring the mass, then heating in an oven at 110 ° C. for 30 minutes, and measuring the mass again. The amount of solvent per 1 m ² calculated from this mass difference was defined as the amount of residual solvent.

When the resin used in the polymer layer is an actinic ray curable resin or a thermosetting resin, a curing treatment is required after coating and drying. For example, in the case of an actinic ray curable resin, it is preferable to irradiate ultraviolet rays, and the necessary activity The irradiation time for obtaining the irradiation amount of light is preferably about 0.1 second to 1 minute, and more preferably 0.1 second to 10 seconds from the viewpoint of curing efficiency or work efficiency of the ultraviolet curable resin. Moreover, it is preferable that the illuminance of these actinic ray irradiation parts is 0.05 W / m < ² > to 0.2 W / m < ² >.

  In the winding process 7, a gas barrier laminate film having the structure of the base material / inorganic barrier layer / polymer layer shown in FIG. 1 after drying is formed, wound into a roll, and stored. Thereafter, when an inorganic barrier layer is further formed on the polymer layer, the inorganic barrier layer is formed by an inorganic barrier layer forming apparatus.

  Next, in the method for producing a barrier film of the present invention, an example of an atmospheric pressure plasma film forming apparatus used for forming an inorganic barrier layer will be described with reference to FIGS.

  As described in, for example, Japanese Patent Laid-Open No. 2000-246091 and Japanese Patent Laid-Open No. 2003-238713, the atmospheric pressure plasma CVD method is used to form a thin film forming gas and a discharge in the discharge space under atmospheric pressure or in the vicinity thereof. In this method, a thin film is formed by supplying a gas containing a gas, exciting the gas by applying a high-frequency electric field to the discharge space, and exposing the gas to the excited gas.

  The atmospheric pressure plasma CVD method used for forming the inorganic barrier layer according to the method for producing a barrier film of the present invention is a plasma CVD method performed under atmospheric pressure or a pressure in the vicinity thereof. The atmospheric pressure or the pressure in the vicinity thereof is about 20 kPa to 110 kPa. In the present invention, 93 kPa to 104 kPa is preferable.

  Hereinafter, an apparatus for forming an inorganic barrier layer using atmospheric pressure plasma CVD near atmospheric pressure will be described.

  FIG. 3 is a schematic view showing an example of a jet type atmospheric pressure plasma film forming apparatus.

  A jet type atmospheric pressure plasma film forming apparatus includes a plasma discharge processing apparatus, an electric field applying means having two power supplies, and a gas supply means (not shown) and an electrode temperature adjusting means (not shown). It is.

  The atmospheric pressure plasma deposition apparatus 8 has a counter electrode composed of a first electrode 801 and a second electrode 802, and the frequency from the first power source 803 is between the first electrode 801 and the counter electrode. A first high frequency electric field of ω1, electric field strength V1, and current I1 is applied, and a second high frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 804 is applied from the second electrode 802. It has become like that. The first power source 803 can apply a higher frequency electric field strength (V1> V2) than the second power source 804, and the first frequency ω1 of the first power source 803 can apply a lower frequency than the second frequency ω2 of the second power source 804. I can do it.

  A first filter 805 is installed between the first electrode 801 and the first power source 803 to facilitate the passage of current from the first power source 803 to the first electrode 801, and the current from the second power source 804. Is designed so that the current from the second power source 804 to the first power source 803 is difficult to pass.

  In addition, a second filter 806 is installed between the second electrode 802 and the second power source 804 to facilitate passage of current from the second power source 804 to the second electrode, and from the first power source 803. The current is grounded so that the current from the first power source 803 to the second power source is difficult to pass.

  A gas G is introduced from the gas supply means as shown in FIG. 4 into the space (discharge space) 807 between the counter electrodes of the first electrode 801 and the second electrode 802, and then from the first electrode 801 and the second electrode 802. A discharge is generated by applying a high-frequency electric field, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper), and the processing space created by the lower surface of the counter electrode and the base material E A thin film is formed on the substrate E in the vicinity of the processing position 808.

  As the substrate E, it is possible to use a flexible belt-shaped substrate or a single-wafer substrate.

  Reference numerals 809 and 810 denote high-frequency voltage probes, and 811 and 812 denote oscilloscopes. The high-frequency voltage probes 809 and 810 and the oscilloscopes 811 and 812 can measure the high-frequency electric field strength (applied electric field strength) and the discharge start electric field strength.

  During the formation of the thin film, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur.

  A plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses are arranged in series and arranged in series and can discharge the gas in the same plasma state at the same time, so that they can be processed many times and processed at high speed. Different layers can also be formed if each device jets different plasma gases.

  FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma film forming apparatus in which a substrate is processed between opposing electrodes.

  In the figure, 9 indicates an atmospheric pressure plasma film forming apparatus. The atmospheric pressure plasma film forming apparatus 9 is an apparatus having at least a plasma discharge processing apparatus 9a, an electric field applying means 9b having two power supplies, a gas supplying means 9c, and an electrode temperature adjusting means 9d.

  The atmospheric pressure plasma film forming apparatus 9 includes a plasma discharge processing apparatus 9a, a counter electrode (discharge space) 9a3 between a roll rotating electrode (first electrode) 9a1 and a square tube type fixed electrode (second electrode) 9a2 group, F is subjected to plasma discharge treatment to form a thin film.

  The plasma discharge processing apparatus 9a forms a single electric field with a pair of rectangular tube-shaped fixed electrodes (second electrodes) 9a2 and a roll rotating electrode (first electrode) 9a1. A carbon atom number concentration layer is formed.

  The roll rotating electrode (first electrode) 9a1 receives the first high-frequency electric field of the frequency ω1, the electric field strength V1, and the current I1 from the first power source 9b1, and the square tube fixed electrode (second electrode) 9a2 group includes the second high-frequency electric field. A second high frequency electric field of frequency ω2, electric field strength V2, and current I2 is applied from the power source 9b2.

  A first filter 9b3 is installed between the roll rotation electrode (first electrode) 9a1 and the first power supply 9b1, and the first filter 9b3 is transferred from the first power supply 9b1 to the roll rotation electrode (first electrode) 9a1. Is designed so that the current from the second power source 9b2 is grounded and the current from the second power source 9b2 to the first power source 9b1 is difficult to pass. A second filter 9b4 is provided between the square tube fixed electrode (second electrode) 9a2 group and the second power source 9b2, and the second filter 9b4 is square tube type from the second power source 9b2. Designed to facilitate the passage of current to the fixed electrode (second electrode) 9a2 group, ground the current from the first power supply 9b1, and make it difficult to pass the current from the first power supply 9b1 to the second power supply 9b2. Has been.

  The roll rotation electrode 9a1 may be the second electrode, and the square tube fixed electrode 9a2 group may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. The current I1 of the first high-frequency electric field is preferably 0.3 mA / cm ² to 20 mA / cm ² , more preferably 1.0 A / cm ² to 20 mA / cm ² . The current I2 of the second high-frequency electric field is preferably 10 A / cm ² to 100 mA / cm ² , more preferably 20 A / cm ² to 100 mA / cm ² .

  The gas G generated by the gas generator 9c1 of the gas supply means 9c is introduced into the plasma discharge treatment vessel 9a4 from the air supply port while controlling the flow rate.

  The substrate F is unwound from the original winding (not shown) or conveyed, or is conveyed from the previous process, and the air or the like that is accompanied by the substrate F by the nip roll 9f through the guide roll 9e. The roll rotation electrode (first electrode) 9a1 and the square tube type fixed electrode (second electrode) 9a2 group are cut off and transferred between the square tube type fixed electrode 9a2 group while winding while being in contact with the roll rotation electrode 9a1. And an electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 9a3.

  The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 9a1. The substrate F passes through the nip roll 9g and the guide roll 9h, and is wound up by a winder (not shown) or transferred to the next step. The treated exhaust gas G ′ that has been discharged is discharged from the exhaust port 9a5.

  During the thin film formation, in order to heat or cool the roll rotating electrode (first electrode) 9a1 and the square tube type fixed electrode (second electrode) 9a2 group, a medium whose temperature is adjusted by the electrode temperature adjusting means 9d is fed. The pump P is sent to both electrodes via the pipe 9d1, and the temperature is adjusted from the inside of the electrode. Reference numerals 9a6 and 9a7 denote partition plates that partition the plasma discharge treatment vessel 9a4 from the outside.

  The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. Say that.

  When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing, it is preferably 0.1 mm to 20 mm, particularly preferably 0.5 mm to 2 mm.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 9a4 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on the metal frame to impart insulation. In FIG. 4, it is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the base material surface) with the material as described above.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus according to the method for producing the water-repellent article of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm ² or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  Moreover, when controlling the film quality of the inorganic barrier layer in the present invention, it can also be achieved by controlling the power on the second power source side.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and particularly preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic spray coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic spray coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above-mentioned item 1 or item 2 and items 5 to 8 are preferable, and item 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, JP-A-2004-68143, 2003-49272, WO 02/48428, etc., in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

After forming the inorganic barrier layer on the substrate, the degassed polymer layer forming coating solution is 20 to 60 ° C. lower than the boiling point of the solvent constituting the polymer layer forming coating solution. The following effects can be given by the method for producing a barrier film that is dried after being applied.
1. A barrier film having a stable gas barrier property can be produced, and the application range to a field requiring a high gas barrier property can be expanded.
2. It has become possible to use it as a base material and sealing material for organic devices such as liquid crystal display elements, solar cells, and organic EL elements that require high gas barrier properties.
3. It has become possible to produce organic devices in a roll-to-roll system that is lighter, larger, and more productive.

  Next, it attaches and demonstrates to the material which concerns on the manufacturing method of the barrier film of this invention.

(Base material)
A base material will not be specifically limited if it is a film formed with the organic material which can hold | maintain the inorganic barrier layer which has barrier property. Specifically, homopolymers such as ethylene, propylene and butene, or polyolefin resins such as copolymers or copolymers, amorphous polyolefin resins such as cyclic polyolefin, polyethylene terephthalate resins, polyethylene-2,6- Polyester resins such as naphthalate, polyamide resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol resins such as polyvinyl alcohol resin and ethylene-vinyl alcohol copolymer, polyimide resins, polyetherimide resins, polysulfone resins Polyether sulfone resin, polyether ether ketone resin, polycarbonate resin, polyvinyl butyrate resin, polyarylate resin, fluorine-based resin, and the like can be used. Among them, polyethylene naphthalate resin such as polyethylene-2,6-naphthalate resin has good gas barrier properties, and particularly oxygen permeability and water vapor permeability are low. Therefore, in the present invention, a polyethylene naphthalate film is used as a substrate. It is preferable to use it.

(Inorganic barrier layer)
In the present invention, the inorganic barrier layer may be a metal carbide, metal nitride, metal oxide, metal sulfide, metal halide, or a mixture thereof (metal oxynitride, metal oxide halide, metal nitride carbide, etc.). Of these, metal oxides are preferred, and specific examples include silicon oxide. The inorganic barrier layer obtained by the atmospheric pressure plasma film-forming apparatus shown in FIGS. 3 and 4 is made of metal by selecting conditions such as organometallic compound, decomposition gas, decomposition temperature, and input power as raw materials (also referred to as raw materials). Carbides, metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof (metal oxynitrides, metal oxyhalides, metal nitride carbides, etc.) can be formed separately, which is preferable.

  For example, silicon oxide can be obtained by using a silicon compound as a raw material compound and oxygen as a decomposition gas, and silicon carbonate is generated by using carbon dioxide as a decomposition gas. Further, if a zinc compound is used as a raw material compound and carbon disulfide is used as a cracked gas, zinc sulfide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it contains a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  Examples of the silicon compound forming the inorganic barrier layer which is such a silicon oxide film include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra-t -Butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane Hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, (Trimethylsilyl) carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, Tetramethyldisilazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di- t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethyl Silane, phenyltrimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclo Examples thereof include tetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate, Erocene, lanthanum isopropoxide, lead acetate, tetraethyllead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain a silicon oxide film, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, Examples thereof include nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various silicon carbides, silicon nitrides, silicon oxides, silicon halides, and silicon sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

(Polymer layer)
The polymer layer is a layer mainly composed of an inorganic polymer, an organic polymer, an organic-inorganic hybrid polymer, or the like.

  The inorganic polymer applicable in the present invention is a film having an inorganic skeleton as a main structure and containing an organic component, and includes a polymer obtained by polymerizing an organometallic compound. These inorganic polymers are not particularly limited, and for example, silicon compounds such as silicone and polysilazane, titanium compounds, aluminum compounds, boron compounds, phosphorus compounds, and tin compounds can be used.

  The silicon compound that can be used in the present invention is not particularly limited, but is preferably tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltrimethyl. Ethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldi Vinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoro Propyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxy Silane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, diaryldimethoxysilane, butyldimethoxy Vinylsilane, trimethyl-3-vinylthiopropylsilane, phenyltrimethylsilane, Methoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyl Trimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryl Loxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibut Xydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, di Acetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane , Octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethylbiphenyl Silane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,3,3- Tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) tetramethyldi Siloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotri Siloxane, octamethylcyclotetrasiloxane, 1, 3, 5, - tetraethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, and the like.

  As the organic polymer, a known polymerizable organic compound can be used. Among them, a polymerizable ethylenically unsaturated bond-containing compound having an ethylenically unsaturated bond in the molecule is preferable, and a general radical is used. It is possible to use polymerizable monomers, polyfunctional monomers and polyfunctional oligomers having a plurality of addition-polymerizable ethylenic double bonds in a molecule generally used for resins that are cured by light, heat, ultraviolet rays, etc. I can do it.

  These polymerizable ethylenic double bond-containing compounds are not particularly limited, but preferred are acrylate polymers and methacrylate polymers. For example, 4-hydroxybutyl acrylate (HBA), 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methyl methacrylate (2-HEMA), glycerol acrylate, Tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, acrylate of 1,3-dioxane alcohol ε-caprolactone adduct, 1,3-dioxolane Monofunctional acrylic esters such as acrylates, or these acrylates with methacrylates, itaconates, crotonates , Methacrylic acid instead of maleate, itaconic acid, crotonic acid, maleic acid ester such as ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, Neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of neopentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2 -Hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate Bifunctional acrylic esters such as tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl ether of 1,6-hexanediol, or methacrylates of these acrylates Methacrylic acid, itaconic acid, crotonic acid, maleic acid ester instead of itaconate, crotonate, maleate, for example, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol triacrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, etc. Examples thereof include polyfunctional acrylic acid esters, or methacrylic acid, itaconic acid, crotonic acid, maleic acid esters in which these acrylates are replaced with methacrylate, itaconate, crotonate, and maleate.

  Prepolymers can also be used as described above. A prepolymer may use together 1 type, or 2 or more types, and may mix and use the above-mentioned monomer and / or oligomer.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  Moreover, as an organic polymer applicable to the polymer layer according to the present invention, it can be easily formed by using a plasma polymerizable organic substance as a thin film forming gas. Examples of the plasma-polymerizable organic substance include hydrocarbons, vinyl compounds, halogen-containing compounds, and nitrogen-containing compounds.

  Examples of the hydrocarbon include ethane, ethylene, methane, acetylene, cyclohexane, benzene, xylene, phenylacetylene, naphthalene, propylene, camphor, menthol, toluene, isobutylene, and the like.

  Examples of the vinyl compound include acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, allyl methacrylate, acrylamide, styrene, α-methyl styrene, vinyl pyridine, vinyl acetate, vinyl methyl ether, and the like.

  Examples of halogen-containing compounds include tetrafluoromethane, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl methacrylate.

  Examples of the nitrogen-containing compound include pyridine, allylamine, butylamine, acrylonitrile, acetonitrile, benzonitrile, methacrylonitrile, aminobenzene and the like.

  Examples of the organic-inorganic hybrid polymer according to the present invention include a film in which an inorganic (organic) material is dispersed in an organic (inorganic) polymer, and a film having both an inorganic skeleton and an organic skeleton as a main structure. The organic-inorganic hybrid polymer that can be applied to the present invention is not particularly limited, but it is preferable to use a combination of the aforementioned inorganic polymer and organic polymer as appropriate.

  Examples of the solvent used in the coating solution for forming the polymer layer used for forming the polymer layer include the following organic solvents, which can be appropriately selected according to the type of the polymer used. Examples of the organic solvent include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, acetic acid). Ethyl, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%. These components are preferably added in the range of 0.01% by mass to 3% by mass with respect to the solid component in the coating solution.

  The water-soluble polymer may be any natural, synthetic, or semi-synthetic water-soluble polymer, and examples thereof include cellulose derivatives such as polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, and carboxymethyl cellulose, or sodium alginate. As the water-soluble polymer, polyvinyl alcohol is particularly preferable.

  Examples of the particles having an average particle size of 7 nm to 100 nm added to the coating solution for forming the polymer layer used for forming the polymer layer include particles such as inorganic oxide, inorganic nitride, and inorganic oxynitride. . Alternatively, organic particles such as polystyrene and PMMA, or hybrid particles of an inorganic compound and an organic compound may be used.

  Specifically, inorganic oxides include silicon oxide, aluminum oxide, titanium oxide, indium oxide, tantalum oxide, zinc oxide, magnesium oxide, tin oxide, zirconium oxide, calcium oxide, boron oxide, strontium oxide, barium oxide, and oxide. Lead, sodium oxide, lithium oxide, potassium oxide and the like can be mentioned.

  Examples of the inorganic nitride include silicon nitride, aluminum nitride, titanium nitride, and silicon carbonitride. Examples of the inorganic oxynitride include silicon oxynitride. These may be used alone or in combination of two or more. Moreover, a mixed system of an inorganic oxide and an inorganic nitride may be used.

  Among these, at least one kind of particles selected from the group consisting of silicon oxide, aluminum oxide, and titanium oxide is preferably used.

  Moreover, as the above-mentioned particles, metal particles whose surfaces are oxidized can also be used. Specifically, the metals include In, Al, Ti, Ta, Zn, Sn, Y, Ge, Pb, Zr, alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca, Sr, Ba). ) And the like.

  Further, the average particle diameter of the particles only needs to be able to close the cracks and defects of the inorganic layer, and specifically, preferably in the range of 7 nm to 100 nm, more preferably 7 nm to 50 nm, Preferably it is in the range of 7 nm to 20 nm. If the average particle size is too small, production such as dispersion is difficult, and if the average particle size is too large, it is difficult to block defects in the inorganic barrier layer.

  The average particle diameter can be confirmed by a scanning electron microscope (SEM) observation photograph (high magnification).

  For mixing the particles into the coating solution, a sol liquid may be mixed, or the particle powder may be dispersed in the coating solution or dispersion. As a dispersion method, a known method such as an ultrasonic dispersion method, a wet dispersion method, or a pressure dispersion method can be appropriately used.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the present invention is not limited to these.

Example 1
(Preparation of base material)
A polyethylene naphthalate film (Teonex QF65 manufactured by Teijin DuPont Co., Ltd.) having a thickness of 100 μm, a width of 200 mm, and a length of 100 m was prepared.

(Formation of inorganic barrier layer)
A 50 nm thick SiO ₂ layer was formed on a polyethylene naphthalate film prepared under the following conditions using the atmospheric pressure plasma discharge treatment apparatus shown in FIG.

  The thickness indicates a value obtained by measurement using MXP21 (manufactured by Mac Science).

Film formation conditions <Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 10W / cm ²
<Electrode conditions>
Two plate-like electrodes are used, and the gap between the electrodes is set to 1 mm. A discharge is formed in the gap, and plasma is ejected from the electrodes toward the substrate surface, whereby the substrate surface is plasma treated. The base material of the plate electrode is stainless steel (SUS304), but ceramic is sprayed on the surface with a thickness of 1 mm. A cooling refrigerant (water) was passed through the electrode at a temperature of 25 ° C. for discharging.

<Gas conditions>
TEOS (tetraethoxysilane) was vaporized by bubbling as a source gas and supplied to the discharge space, and a SiO ₂ layer was formed on the surface of the substrate by utilizing a decomposition reaction by plasma energy.

Discharge gas: Nitrogen gas 2 slm / cm
Reaction gas: Oxygen gas 0.01 slm / cm
Gas for forming a thin film: 200 ml of TEOS raw material is prepared in a 500 ml glass bubbling container and kept at 25 ° C. Argon gas of 0.05 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

(Manufacture of barrier films)
(Preparation of coating solution for polymer layer formation)
To 10 g of trifunctional isocyanuric acid ethylene oxide-modified triacrylate (Aronix M-315: manufactured by Toagosei Co., Ltd.), a radical initiator (Irgacure 651: manufactured by Ciba Geigy) was added in an amount equivalent to 1% by mass of Aronix M-315, A polymer film-forming coating solution was prepared by dissolving in 250 g of methyl ethyl ketone. This coating solution was liquid at room temperature (25 ° C.).

(Deaeration of coating solution for polymer layer formation)
The prepared coating solution for forming a polymer layer was used at a temperature of 25 ° C. using a membrane degassing module (DICESEL PFF manufactured by DIC Corporation), and the degassing degree was set to 30%. The degree of deaeration was determined by determining the ratio of dissolved oxygen amount / saturated dissolved oxygen amount after deaeration to the ratio of the dissolved air amount in the polymer layer forming coating solution to the saturated air dissolved amount. As the amount of dissolved oxygen, a value measured by CD-200SC manufactured by HORIBA Ltd. was used.

(Formation of polymer layer)
Using the manufacturing process shown in FIG. 2, the polymer layer-forming coating solution is applied to the polyethylene naphthalate film on which the inorganic barrier layer has been formed by changing the temperature as shown in Table 1 and using an extrusion coater. A barrier film was prepared by forming a polymer layer having a dry film thickness of 2 μm. 101 to 105. The temperature of the degassed polymer layer forming coating solution at the time of coating indicates the temperature relative to the boiling point of the solvent constituting the polymer layer forming coating solution.

  In addition, sample no. No. 102 was applied and dried under the same conditions to form a polymer layer, and a barrier film was prepared. 106.

Evaluation Each sample No. Table 1 shows the results obtained by measuring the oxygen transmission rate, water vapor transmission rate, and storage stability in accordance with the evaluation ranks shown below.

Method for Measuring Oxygen Permeability Oxygen permeability was measured according to a method specified in JIS K 7126B.

Evaluation rank of oxygen permeability ◎: 0.005ml ^/ m less than 2 · 24h · atm ○: 0.01ml / m less than ^{2 · 24h · atm, 0.005ml /} m 2 · 24h · atm or more △: 0.1ml / Less than m ² · 24h · atm, 0.01ml / m ² · 24h · atm or more ×: 0.1ml / m ² · 24h · atm or more Measurement method of water vapor transmission rate Water vapor transmission according to the method specified in JIS K7129B The rate was measured. As a result, all the samples were 0.01 g / m ² · day or less.

Evaluation rank of the water vapor transmission rate ◎: 0.005g ^/ m less than 2 · 24h ○: 0.01g ^/ m less than ^{2 · 24h, 0.005g / m 2} · 24h or more △: 0.1 ^/ m less than 2 · 24h, 0.01 g / m ² · 24 h or more ×: 0.1 g / m ² · 24 h or more Preservability evaluation method Each of the gas barrier films produced above was immersed in hot water at 98 ° C. for 48 hours, and then in accordance with JIS K5400. Adhesion was evaluated by a cross cut test. Specifically, 11 cuts were made vertically and horizontally on the gas barrier film forming surface, and 100 1 mm square grids were prepared. A cellophane tape was applied on this, and it was peeled off quickly at an angle of 90 degrees. The presence or absence of was confirmed visually to evaluate the storage stability.

Evaluation rank of storage stability ◎: Not peeled off at all ○: Slight float is observed in some grids, but good quality △: Peeling is observed at 1 and 2 grids, but practically Is an acceptable quality. X: Peeling is observed at 3 or more grids, and is a quality that is practically problematic.

  When producing a barrier film in which an inorganic barrier layer and a polymer layer are laminated in this order on a film substrate, after degassing the polymer layer forming coating solution for forming the polymer layer, the polymer layer forming coating solution is Sample No. produced by coating at a temperature of −20 ° C. to −60 ° C. with respect to the boiling point of the solvent (methyl ethyl ketone). 102 to 104 showed excellent performance in both oxygen permeability and water vapor permeability.

  Sample No. produced by coating at a temperature of −65 ° C. with respect to the boiling point of the solvent (methyl ethyl ketone) constituting the coating liquid for forming the polymer layer. Sample No. 101 of the present invention has both oxygen permeability and water vapor permeability. Results were inferior to 102-104.

  Sample No. produced by coating at a temperature of −15 ° C. with respect to the boiling point of the solvent (methyl ethyl ketone) constituting the coating liquid for forming the polymer layer. No. 105 is a sample having a storage stability of Sample No. Results were inferior to 102-104.

  Sample No. produced without degassing the polymer layer forming coating solution. Sample No. 106 of the present invention has both oxygen permeability and water vapor permeability. Results were inferior to 102-104. The effectiveness of the present invention was confirmed.

Example 2
(Preparation of base material)
The same polyethylene naphthalate film as in Example 1 was prepared.

(Formation of inorganic barrier layer)
A SiO ₂ layer having a thickness of 50 nm was formed on the prepared polyethylene naphthalate film by the same method as in Example 1.

(Manufacture of barrier films)
(Preparation of coating solution for polymer layer formation)
When prepared in Example 1, the same polymer layer forming coating solution as the polymer layer forming coating solution was prepared.

(Deaeration of coating solution for polymer layer formation)
As shown in Table 2, the degree of deaeration was changed. The change of the deaeration degree was adjusted by changing the deaeration time. The degree of deaeration was determined by the same method as in Example 1. The same membrane degassing module as in Example 1 was used for degassing.

Temperature of coating solution for polymer layer formation when degassing: 20 ° C
(Formation of polymer layer)
Using the manufacturing process shown in FIG. 2, the temperature of each coating liquid for forming a polymer layer with a different degree of deaeration as shown in Table 2 is applied to the polyethylene naphthalate film on which the prepared inorganic barrier layer is formed. A barrier film was prepared by applying a coating layer with an extrusion coater at −40 ° C. with respect to the boiling point of the solvent (methyl ethyl ketone) constituting the coating solution to form a polymer layer having a dry film thickness of 2 μm. 201 to 204.

Evaluation The produced barrier film no. Table 2 shows the results obtained by measuring oxygen transmission rate, water vapor transmission rate, and storage stability in the same manner as in Example 1 and evaluating according to the same evaluation rank as in Example 1.

  When producing a barrier film in which an inorganic barrier layer and a polymer layer are laminated in this order on a film substrate, sample No. produced with a degassing degree of the polymer layer forming coating solution forming the polymer layer at 30% or less . Nos. 203 and 204 showed excellent performance in all of oxygen permeability, water vapor permeability, and storage stability. The effectiveness of the present invention was confirmed.

Example 3
(Preparation of base material)
The same polyethylene naphthalate film as in Example 1 was prepared.

(Formation of inorganic barrier layer)
A SiO ₂ layer having a thickness of 50 nm was formed on the prepared polyethylene naphthalate film by the same method as in Example 1.

(Manufacture of barrier films)
(Preparation of coating solution for polymer layer formation)
A material for forming the polymer layer forming coating solution was changed as shown in Table 3 to prepare a polymer layer forming coating solution. 3-1 to 3-6.

Coating liquid for forming polymer layer No. Preparation of 3-1 9 g of tripropylene glycol diacrylate (TPGDA: manufactured by Daicel Cytec) and 0.1 g of a photopolymerization initiator (manufactured by Ciba Japan, Irgacure 907) are dissolved in 250 g of methyl ethyl ketone as a photopolymerizable acrylate. Coating solution.

Coating liquid for forming polymer layer No. 3-2 Preparation As a photopolymerizable acrylate, 9 g of bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Oligo EA-1020) and 0.1 g of a photopolymerization initiator (Ciba Japan, Irgacure 907) were added to methyl ethyl ketone. It was dissolved in 250 g to obtain a coating solution.

Coating liquid for forming polymer layer No. Preparation of 3-3 94 parts of hydroxymethyltricyclodecane dimethacrylate, 6 parts of hydroxymethyltricyclodecane monomethacrylate, 6 parts of β-thiopropionate, 0.1 part of photoinitiator ("Lucirin TPO" manufactured by BASF) , 0.1 part of benzophenone was stirred and mixed uniformly to obtain a coating solution no. 3-3 was obtained.

Coating liquid for forming polymer layer No. Preparation of 3-4 A separable four-necked flask was equipped with a temperature control regulator, a cooling tube, and a stirring device, charged with 70 parts of purified water, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Hereafter, 30 parts of GLM (Nippon Yushi Co., Ltd., “Blemmer GLM”), 20 parts of purified water, 0.3 part of azo compound (“V-50” manufactured by Wako Pure Chemical Industries, Ltd.) take 1 hour. And dripped. After completion of dropping, the reaction was continued for another 3 hours. After completion of the polymerization, 81 parts of purified water was added with sufficient stirring to obtain a polyglycerol methacrylate aqueous solution having a solid content of 15%.

Coating liquid for forming polymer layer No. Preparation of 3-5 As a water-soluble polymer, 50 parts by mass of polyvinyl alcohol and 50 parts by mass of tetraethoxysilane were added with a diluting solvent (water / methanol mixed solvent) and a hydrolysis catalyst (0.1 mol / 1 HCl solution), stirred and applied. Liquid No. 3-5 was obtained.

Coating liquid for forming polymer layer No. Preparation of 3-6 Polysilazane 20 mass% xylene solution ("NL110A" manufactured by AZ Electronic Materials Co., Ltd.) It was set to 3-6.

(Deaeration of coating solution for polymer layer formation)
Each of the prepared coating solutions for polymer layer formation No. Degassing was performed using the same degassing method and conditions as in Example 1 from 3-1 to 3-6, and the degassing degree was 50%.

(Formation of polymer layer)
Using the manufacturing process shown in FIG. 2, the temperature of each coating liquid for forming a polymer layer with different constituent materials as shown in Table 3 is applied to the polyethylene naphthalate film on which the prepared inorganic barrier layer is formed. A barrier film was prepared by applying a coating layer with an extrusion coater at −40 ° C. with respect to the boiling point of the solvent constituting the liquid to form a polymer layer having a dry film thickness of 2 μm. 301 to 306.

Evaluation The produced barrier film no. From Table 301 to 306, the oxygen permeability, water vapor permeability, and storage stability were measured by the same method as in Example 1, and the results evaluated according to the same evaluation rank as in Example 1 are shown in Table 4.

  When producing a barrier film in which an inorganic barrier layer and a polymer layer are laminated in this order on a film substrate, the material of the coating solution for forming a polymer layer is an acrylate resin, a methacrylate resin, or a polysilazane. Sample No. prepared and used. Nos. 301 to 306 showed excellent performance in all of oxygen permeability, water vapor permeability, and storage stability. The effectiveness of the present invention was confirmed.

Example 4
(Preparation of base material)
The same polyethylene naphthalate film as in Example 1 was prepared.

(Formation of inorganic barrier layer)
A SiO ₂ layer having a thickness of 50 nm was formed on the prepared polyethylene naphthalate film by the same method as in Example 1.

(Manufacture of barrier films)
(Preparation of coating solution for polymer layer formation)
A coating solution for forming a polymer layer shown below having particles was prepared and 4-1 to 4-8. FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. was used for particle size measurement.

Coating liquid for forming polymer layer No. Preparation of 4-1 Trifunctional isocyanuric acid ethylene oxide modified triacrylate (Aronix M-315: manufactured by Toagosei Co., Ltd.) and a radical initiator (Irgacure 651: manufactured by Ciba Geigy) equivalent to 1% by mass of Aronix M-315 An amount was added and dissolved in 250 g of methyl ethyl ketone. Subsequently, a MEK-ST (particle size 10 nm to 15 nm) solution manufactured by Nissan Chemical Co., Ltd. was mixed with the coating solution so that the particle content was 15 vol%, and stirred to form a coating solution No. 4-1.

Preparation of polymer layer forming coating solution 4-2 to 4-3 Except for changing the particles to be mixed into the polymer layer forming coating solution to MEK-ST (particle size 40 nm to 45 nm and 70 nm to 80 nm) manufactured by Nissan Chemical Co., Ltd. In the same manner as in 4-1, the coating liquid for forming a polymer layer No. 4-2 (using a particle size of 40 nm to 45 nm) was obtained from 4-3 (using a particle size of 70 nm to 80 nm).

Preparation of polymer layer forming coating solution 4-4 Polymer layer forming coating solution in the same manner as in 4-1, except that the particles mixed in the polymer layer forming coating solution are changed to NanoDur X1130PMA (particle size: 45 nm) manufactured by Nanophase Technologies. Liquid No. 4-4 was obtained.

Preparation of polymer layer forming coating solution 4-5 Polymer layer forming coating solution No. 4-1, except that the particles mixed in the polymer layer forming coating solution are changed to Nippon Aerosil AEROSIL RX300 (particle size 7 nm). . 4-5 was obtained.

Preparation of polymer layer forming coating solutions 4-6 and 4-7 In a polyethylene container having an internal volume of 1 L, 700 g of colloidal silica (PL series (particle size 100 nm and 120 nm) manufactured by Fuso Chemical Co., Ltd.) was stirred. Methanol vapor generated in a separate boiler while charging the 1-L glass reactor equipped with a condenser, thermometer and two inlets, maintaining the sol boiling in the reactor and raising the liquid level slightly. Was continuously blown into the silica sol in the reactor. The substitution was terminated when the volume of the distillate reached 10 L, and a methanol-dispersed silica sol (SiO ₂ concentration 15.0% by mass) was obtained. Subsequently, this dispersion was mixed with the coating solution so that the particle content was 15 vol%, and stirred to form a polymer layer forming coating solution No. 4-6 (using a particle size of 100 nm) and 4-7 (using a particle size of 120 nm) were obtained.

Preparation of Polymer Layer Forming Coating Liquid 4-8 Polymer Layer Forming Coating Liquid No. 4-8 was prepared in the same manner as Polymer Layer Forming Coating Liquid 4-1, except that no particles were added. 4-8 was obtained.

(Deaeration of coating solution for polymer layer formation)
Each of the prepared coating solutions for polymer layer formation No. Degassing was performed using the same degassing method and conditions as in Example 1 from 4-1 to 4-8, and the degassing degree was 30%.

(Formation of polymer layer)
Using the production process shown in FIG. 2, each polymer layer forming coating solution No. 1 was prepared by changing the particle size of the particles to be added to the prepared polyethylene naphthalate film on which the inorganic barrier layer was formed. The temperature of the coating solution of 4-1 to 4-8 was applied with an extrusion coater at -40 ° C. with respect to the boiling point of the solvent constituting the coating solution for forming a polymer layer, and a polymer layer having a dry film thickness of 2 μm was formed. A barrier film was formed and sample no. 401 to 408.

Evaluation The produced barrier film no. From Table 401 to 408, oxygen permeability, water vapor permeability, and storage stability were measured by the same method as in Example 1, and the results of evaluation according to the same evaluation rank as in Example 1 are shown in Table 5.

  When a barrier film is formed by laminating an inorganic barrier layer and a polymer layer in this order on a film substrate, particles having an average particle diameter of 7 nm to 100 nm are added to a coating solution for forming a polymer layer. Sample No. Nos. 401 to 406 showed excellent performance in terms of oxygen permeability, water vapor permeability, and storage stability. The effectiveness of the present invention was confirmed.

DESCRIPTION OF SYMBOLS 1 Barrier film 101, 301, E, F Base material 102 Inorganic barrier layer 103 Polymer layer 2 Manufacturing process 3 Base material supply process 4 Polymer layer formation coating liquid supply process 401 Polymer layer formation coating liquid storage tank 402 Deaerator 403 Heating device 5 Coating process 501 Coater 502 Backup roll 6 Drying process 7 Winding process 8, 9 Atmospheric pressure plasma film forming apparatus 801 First electrode 802 Second electrode 9a1 Roll rotating electrode 9a2 Square tube fixed electrode

Claims (6)

In the method for producing a barrier film having at least one inorganic barrier layer and at least one polymer layer on the film substrate,
When applying and forming a polymer layer forming coating solution on the inorganic barrier layer by a coating method,
After degassing the polymer layer forming coating solution, the barrier layer is applied at a temperature lower by 20 to 60 ° C. than the boiling point of the solvent constituting the polymer layer forming coating solution. Production method.   The method for producing a barrier film according to claim 1, wherein the polymer layer forming coating solution has a degassing degree of 30% or less.   The method for producing a barrier film according to claim 1 or 2, wherein the polymer layer is formed of an acrylate resin or a methacrylate resin.   The method for producing a barrier film according to claim 1, wherein the polymer layer is formed of polysilazane.   The method for producing a barrier film according to any one of claims 1 to 4, wherein the polymer layer includes particles having an average particle diameter of 7 nm to 100 nm.   The method for producing a barrier film according to any one of claims 1 to 5, wherein the inorganic barrier layer is a silicon oxide-based barrier film formed by an atmospheric pressure plasma method.

Images