JP2012116960A - Gas barrier film, method for producing the same, and organic electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which can be produced inexpensively with high productivity, having high gas barrier property, capable of maintaining high gas barrier property even after bending or after preservation with passage of time, and to provide a method for producing the gas barrier film, and an organic electronic device having the gas barrier film.SOLUTION: In the method for producing the gas barrier film having a gas barrier layer containing a metal oxide, a material reactable with water is brought into contact with a gas barrier layer surface with the gas barrier film placed under an environment having an absolute humidity of 0.001-3 g/m.

Description

  The present invention mainly relates to a gas barrier used for a display material such as a package such as an electronic device, or an organic photoelectric conversion element (organic solar battery), an organic electroluminescence element (hereinafter also referred to as an organic EL element), and a plastic substrate such as a liquid crystal. The present invention relates to a conductive film, a method for producing a gas barrier film, and an organic electronic device having the gas barrier film.

  Conventionally, a gas barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging of goods and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals.

  In addition to packaging applications, they are used in liquid crystal display elements, photoelectric conversion elements (solar cells), organic electroluminescence (organic EL) substrates, and the like.

  Aluminum foil or the like is widely used as a packaging material in the field of such a liquid crystal display element or the like, but disposal treatment after use is a problem. In addition, aluminum foil, etc. is basically opaque and has the problem that the contents cannot be confirmed from the outside. Furthermore, transparency is required for solar cell materials, and it is applied. I can't.

  In particular, transparent substrates that have been applied to liquid crystal display elements, organic EL elements, photoelectric conversion elements, and the like have recently been required to be lightweight and large. In addition to these requirements, advanced requirements such as being capable of roll-to-roll production, high long-term reliability and high degree of freedom in shape, and the ability to display curved surfaces are added, resulting in heavy and cracking. Instead of thick glass substrates that are easy to increase in area, film base materials such as transparent plastics have begun to be used.

  However, a film substrate such as a transparent plastic has a problem that the gas barrier property is inferior to glass. For example, when used as a material for an organic photoelectric conversion element, if a base material with poor gas barrier properties is used, water vapor or air penetrates and the organic film deteriorates, which becomes a factor that impairs photoelectric conversion efficiency or durability.

  In addition, when a film substrate such as plastic is used as a substrate for an electronic device, oxygen permeates the substrate and penetrates and diffuses into the electronic device, and the device is deteriorated or required in the electronic device. This causes a problem that the degree of vacuum cannot be maintained.

  For packaging materials and the like, gas barrier films using organic polymer compounds such as polyvinylidene chloride and liquid crystalline polyester, which are considered to have relatively gas barrier properties, are known. However, although a gas barrier film composed only of organic materials has high flexibility and bending resistance, its gas barrier properties are limited, and it is virtually impossible to obtain high barrier properties applicable to electronic device applications. It is said.

  In order to solve such problems, it is known to form a gas barrier film substrate by forming an inorganic film such as a metal oxide thin film on a film substrate. As gas barrier films used for packaging materials and liquid crystal display elements, those obtained by depositing silicon oxide or aluminum oxide on plastic films are known.

  In addition, a stable plasma discharge with a high energy density as a method for forming a gas barrier layer by atmospheric pressure plasma CVD, which can be formed under atmospheric pressure, rather than vapor deposition, CVD, sputtering, etc. that require a vacuum process. There has also been proposed a film forming method capable of satisfying the requirements (for example, see Patent Document 1 and Patent Document 2).

  In the above Patent Documents 1 and 2, in order to prevent cracking when a silica film having a high gas barrier property is formed on a flexible plastic film such as polyethylene terephthalate (PET), A stress relaxation design is performed in which the carbon component is distributed and the hardness of the film decreases toward the base material. According to this method, while it is possible to form a high gas barrier film that prevents the occurrence of cracks, it is necessary to carry out film formation at an ultra-low speed in order to obtain a dense barrier film. Have the problem of becoming expensive.

  On the other hand, as a method capable of forming a film by a simple coating process, a gas barrier layer made of a converted silica film is formed by subjecting a film obtained by applying a coating solution of a silicon compound such as polysilazane onto a substrate. Some methods are also known (see, for example, Patent Document 3, Patent Document 4, and Patent Document 5).

Patent Document 3 discloses a process for converting a polysilazane coating film into a silica film by an oxygen plasma discharge treatment under atmospheric pressure, and a gas barrier layer can be formed without requiring a vacuum process. However, the water vapor transmission rate of the obtained film is 0.35 g / (m ² · 24 h), which cannot be said to be a gas barrier layer applicable to the device as described above. Generally, it is said that the water vapor transmission rate of a gas barrier layer required for application to an organic photoelectric conversion element needs to be significantly lower than 1 × 10 ⁻² g / (m ² · 24 h).

  On the other hand, Patent Documents 4 and 5 disclose a method of irradiating a polysilazane coating film with ultraviolet rays as a method of forming a dense silica film by converting polysilazane. According to this method, since it is thought that the reaction proceeds by direct oxidation without going through dehydration condensation, silica conversion at a lower temperature becomes possible, and a very effective method for forming a gas barrier layer on a resin film. It can be said. However, even when the precursor coating film is converted to form a silica film, in order to obtain gas barrier properties, an inorganic film is used to obtain a gas barrier property, as in the case of the vapor deposition method, the sputtering method, the plasma CVD method, etc. It has been found through repeated examination that the occurrence of defects such as cracks and pinholes cannot be avoided by simply increasing the film thickness, and the desired gas barrier properties cannot be obtained.

  As one of the solutions to the problem of such cracking, a method of providing an intermediate layer such as a resin between gas barrier layers is conceivable. However, due to an increase in the cost due to the increase in the number of coating film processes and an adhesion failure with the inorganic gas barrier layer. There are concerns about performance degradation, process resistance degradation, performance degradation due to gas permeation from the intermediate layer side, and the current situation is that it is difficult to achieve both low cost and high barrier properties.

  In view of the above, in order to develop a gas barrier film satisfying all of cost reduction, high barrier properties, and flexibility (bending resistance), it is necessary to develop a method for producing an inorganic film having high bending resistance and no defects. It can be said that it is essential.

  However, if it is practically impossible to form a complete inorganic film with no defects, the development of a defect repair technology for inorganic films is the shortcut to the development of low-cost high-barrier films. It is no exaggeration to say.

  As a technique having such a viewpoint, for example, Patent Document 6 is cited. Patent Document 6 discloses a barrier film having a sealing layer containing reactive nanoparticles that interact with moisture and oxygen through gas barrier layer defects.

  In the barrier film of Patent Document 6, it is anticipated that the inert nanoparticle will fill the defect, but it is practically impossible to completely fill it, and even if it is buried, there is a gap between the particle and the defect. A sufficient repair effect is not expected. In this way, since substantial defects remain in the gas barrier layer, it is conceivable that moisture that has entered from the outside in the film will remain over time. In the case of sealing, there is a high possibility that an extra step such as baking is increased. Furthermore, there is also a concern that, due to the remaining defect, a crack spreads from the defect at the time of bending, which causes deterioration of bending resistance.

  In addition, since a reactive nanoparticle layer, that is, a moisture trap layer, is present as a constituent element, there is a concern that the moisture trap ability may decrease with time, which may lead to a decrease in gas barrier properties. Furthermore, if the reactive nanoparticle layer retains moisture and exceeds the limit, there is a possibility that the gas barrier layer may be rapidly broken.

  Thus, since it is insufficient as a defect repair technique for the inorganic barrier layer, a multi-layer structure is unavoidable in order to obtain a high barrier property, that is, it is difficult to achieve a reduction in cost.

  Moreover, in patent document 4, there is a description of a process of contacting a mixed solution of alkoxysilane and water, that is, a sol-gel silica forming material, as an additional treatment to the polysilazane conversion film. If this method is used, it is expected that defects on the barrier layer surface will be completely repaired. However, since there is adsorption of excess moisture, the baking process is performed before sealing electronic devices and the like, as in Patent Document 6. Etc. are required, which is not preferable in terms of cost.

  Further, since it is considered that moisture remains in the gas barrier layer in a state where the surface defects are blocked, there is a concern that excessive stress is applied to the inside of the gas barrier layer and the gas barrier layer is destroyed.

  As described above, there is currently no method for producing a barrier film having a low cost and high stability over time and bending resistance.

JP 2004-84027 A JP 2008-56967 A JP 2007-237588 A Japanese Patent Laid-Open No. 10-279362 JP 2008-159824 A International Publication No. 08/57045 Pamphlet

  An object of the present invention is to provide a gas barrier film that has a high gas barrier property, maintains a high gas barrier property even after bending or storage with time, can be produced at a high productivity and at a low cost, a method for producing the same, and an organic material having the gas barrier film. To provide an electronic device.

  In the present invention, by the gas barrier film manufacturing method using a process technology for selectively repairing defects in the inorganic barrier film, the gas barrier film has a high gas barrier property and maintains a high gas barrier property even after bending or storage over time, An organic electronic device having the gas barrier film could be provided at low cost with high productivity.

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

1. In the method for producing a gas barrier film having a gas barrier layer containing a metal oxide, the gas barrier film is brought into contact with the surface of the gas barrier layer with a material that reacts with water in an environment where the absolute humidity is 0.001 to ³ g / m ^3. A method for producing a gas barrier film, characterized by comprising:

2. 2. The gas barrier film according to 1, wherein the gas barrier film is exposed to an environment having an absolute humidity of 5 to 120 g / m ³ before the material that reacts with water contacts the surface of the gas barrier layer. Production method.

  3. 3. The method for producing a gas barrier film as described in 1 or 2 above, wherein the material that reacts with water forms a metal oxide having an OMO bond by hydrolysis. However, M represents Si, Ti, Al, Zr or Mg.

  4). 4. The method for producing a gas barrier film as described in 3 above, wherein the metal oxide has a hydroxyl group.

  5). 5. The energy according to any one of 1 to 4, wherein energy is imparted to the gas barrier layer when the material that reacts with water is in contact with the surface of the gas barrier layer or after the material is contacted. Of producing a gas barrier film.

  6). A gas barrier film produced by the method for producing a gas barrier film according to any one of 1 to 5 above.

  7). 7. An organic electronic device sealed with the gas barrier film described in 6 above.

  INDUSTRIAL APPLICABILITY According to the present invention, a gas barrier film having a high gas barrier property, maintaining a high gas barrier property even after being bent or stored over time, having a high productivity and capable of being manufactured at low cost, a method for producing the same, and an organic electronic device having the gas barrier film Could be provided.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with the photoelectric converting layer of the three-layer structure of p-i-n. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is a schematic sectional drawing which shows the defect repair process of the gas barrier film of this invention.

As a result of intensive studies in view of the above problems, the present inventor, as a result, in the method for producing a gas barrier film having a gas barrier layer containing a metal oxide, the gas barrier film has an absolute humidity of 0.001 to ³ g / m ³ . In the environment, the gas barrier film manufacturing method in which a material that reacts with water is brought into contact with the surface of the gas barrier layer has a high gas barrier property, maintains a high gas barrier property even after bending and storage over time, and is highly productive and inexpensive. It has been found that a method for producing a gas barrier film that can be produced is obtained and the present invention has been achieved.

The present invention discloses a process technique for selectively repairing defects in a gas barrier layer (film) containing a metal oxide. Specifically, moisture diffused in the gas barrier layer is induced to the surface through cracks, pinholes, etc., and in a low humidity environment where the material reacts with water and the absolute humidity is 0.001 to ³ g / m ^3. In other words, it can be rephrased as a technique of filling defects while trapping water.

  Hereinafter, the present invention, its components, and embodiments for carrying out the present invention will be described in detail.

[Method for producing gas barrier film]
First, the method for producing the gas barrier film of the present invention will be described.

The present invention relates to a method for producing a gas barrier film having a gas barrier layer containing a metal oxide, and the material that reacts with water in an environment having an absolute humidity of 0.001 to ³ g / m ^3. Is brought into contact with the surface of the gas barrier layer.

As the gas barrier property of the gas barrier film of the present invention, the water vapor permeability measured according to the JIS K 7129B method (water vapor permeability: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is 9 × 10 ⁻ It is preferably ⁴ g / (m ² · 24 h) or less, more preferably 9 × 10 ⁻⁵ g / (m ² · 24 h) or less.

The oxygen permeability (oxygen permeability) measured by a method according to JIS K 7126-1987 is preferably 0.01 ml / (m ² · 0.1 MPa / day) or less, more preferably 0.8. 001 ml / (m ² · 0.1 MPa / day) or less.

  Subsequently, the present invention will be described in more detail.

[Gas barrier layer]
<Metal oxide>
The gas barrier layer in the gas barrier film of the present invention is characterized by containing a metal oxide.

  Examples of the metal oxide contained in the gas barrier layer of the present invention include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tantalum oxide, tin oxide, vanadium oxide, and indium tin oxide (ITO). However, it is not limited to these, and it may be composed of one kind of metal oxide or a composite material composed of two or more kinds of metal oxides. Further, in addition to the metal oxide, an inorganic substance such as a metal nitride, a metal oxynitride, or a metal may be further included.

  As the metal oxide of the present invention, a silicon oxide compound is preferable and silicon dioxide is more preferable in that a denser film with fewer defects can be formed.

  Here, the silicon dioxide in the present invention includes an atomic composition ratio in the range of Si: O = 1: 1.8 to 2.2, and further includes N atoms in Si: N = 1: 0.01 to It may contain about 0.2.

  A method for forming the gas barrier layer according to the present invention is not particularly limited, but a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, a large size, and the like. Examples include dry processes such as the atmospheric pressure plasma method, spray coating methods, spin coating methods, blade coating methods, dip coating methods, casting methods, roll coating methods, bar coating methods, die coating methods, and other coating processes. It can be selected as appropriate.

  Among these, as the dry process, the atmospheric pressure plasma method is preferable because a roll-to-roll process under atmospheric pressure is possible.

  In addition, the coating process is more preferable because it is highly safe, can be formed easily and at a lower cost.

  When film formation is performed by a coating process, for example, a method of drying after coating a fine particle dispersion of an inorganic oxide, a sol-gel method of forming an inorganic oxide film from a precursor such as an alkoxide body, and the like can be applied. In addition, a method of obtaining a silicon oxide film by applying a conversion treatment to a coating film of silazane compound, siloxane compound, alkylsilane, alkoxysilane, or the like is more preferable because a higher gas barrier property can be easily formed in a short time. . More specifically, polysiloxanes such as perhydropolysilazane, hexamethyldisilazane, silsesquioxane, and hexamethyldisiloxane, tetramethylsilane, trimethylmethoxysilane, tetraethoxysilane, and the like can be given. These materials may contain a catalyst such as amine or metal for accelerating the oxidation reaction, about 0.1 to 10% by mass relative to the solid content, and two or more different materials may be used. You may form a film | membrane using the mixed coating liquid.

  Examples of materials available as perhydropolysilazane in the present invention include Aquamica NN120, NN110, NAX120, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140, etc., manufactured by AZ Electronic Materials Co., Ltd. Examples of materials that can be obtained by OXAN include FOX-14.

  As the coating solution of the composition containing the silazane compound, it is preferable to use a solvent that does not easily contain water, such as xylene, dibutyl ether, solvesso, and terpene, as a solvent in order to prevent the coating solution and moisture from reacting during coating. .

  The coated film is preferably annealed to obtain a uniform dry film from which the solvent has been removed. The annealing temperature is preferably 60 to 200 ° C, more preferably 70 to 160 ° C. The annealing time is preferably about 5 seconds to 24 hours, more preferably about 10 seconds to 2 hours.

  As described above, by performing annealing in the above-described range before the conversion process following the next step, a uniform coating film can be stably obtained.

  The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). In the annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 30 to 90% RH, more preferably 40 to 80% RH.

  The thickness of the gas barrier layer in the present invention is preferably in the range of 30 to 2000 nm, more preferably in the range of 40 to 500 nm, and particularly preferably in the range of 40 to 300 nm.

  Moreover, it is preferable that the gas barrier layer containing the metal oxide according to the present invention has a hydroxyl group particularly in a defective portion of the gas barrier layer. In this case, when repairing a defective part with a material that reacts with water as described later, not only water but also a hydroxyl group present on the side surface of the defective part forms a stronger molecular bond, so a more dense repair effect Is preferable in that it can be expected.

  Here, the gas barrier layer of the present invention containing silicon oxide is formed by applying a conversion treatment (oxidation treatment) to a coating film such as a silazane compound, a siloxane compound, an alkylsilane, or an alkoxysilane, which is a precursor of an inorganic oxide. How to do will be described.

<Conversion processing>
Examples of the method for converting the precursor coating film as described above into a film containing an inorganic oxide include heat treatment, plasma irradiation treatment, and light irradiation treatment, but the conversion reaction proceeds at a relatively low temperature. Thus, plasma irradiation treatment and light irradiation treatment are preferable, and light irradiation treatment is more preferable in that a denser film can be formed in a short time.

<Plasma irradiation treatment>
As the plasma irradiation treatment, a general vacuum oxygen plasma method or the like can be used, but it is preferable to use the atmospheric pressure plasma method because an atmospheric pressure process is possible. In the atmospheric pressure plasma method, oxygen gas or hydrogen gas is used as a reaction gas, for example, by applying a conversion treatment to a coating film formed from a precursor solution containing a silicon compound as described above, for example, silicon oxide The gas barrier layer of the present invention containing a product can be obtained.

<Light irradiation treatment>
As the light irradiation treatment, the light in the light irradiation treatment is more preferably ultraviolet light. Irradiation with ultraviolet light generates active oxygen and ozone, and the oxidation reaction further proceeds.

  Since this active oxygen and ozone are highly reactive, for example, polysilazane, which is a silica precursor, is directly oxidized without passing through silanol, so that it is converted into a silicon dioxide film with higher density and fewer defects. .

  Further, ozone may be generated from oxygen by a known method such as a discharge method at a portion different from the light irradiation portion for the shortage of reactive ozone and introduced into the ultraviolet irradiation portion.

  The wavelength of the ultraviolet light irradiated at this time is not particularly limited, but the wavelength of the ultraviolet light is preferably 100 to 450 nm, and more preferably vacuum ultraviolet light of about 150 to 300 nm is irradiated.

As the light source, a low-pressure mercury lamp, a deuterium lamp, a xenon excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. The output of the lamp ^{400W~30kW, 100mW / cm 2 ~100kW /} cm 2 as illuminance, preferably 10~5000mJ / cm ² as irradiation energy, 100 to 2000 mJ / cm ² is more preferable. Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² .

  Among these, as the wavelength, vacuum ultraviolet light of 100 to 200 nm is most preferable, and the oxidation reaction can be advanced at a lower temperature and in a shorter time. As a light source, a rare gas excimer lamp such as a xenon excimer lamp is most preferably used.

  For example, when polysilazane is irradiated with ultraviolet rays, the polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. The film thickness and density of the silica film can be controlled by the intensity of ultraviolet light, irradiation time, and wavelength (light energy density), and can be appropriately selected, such as using different types of lamps to obtain a desired film structure. Is possible. Further, not only continuous irradiation but also multiple irradiations may be performed, and the multiple irradiations may be so-called pulse irradiation for a short time.

  In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to promote the reaction (also referred to as oxidation reaction, conversion treatment, or modification treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. You may select suitably the method which can maintain the smoothness of a coating film.

  As temperature to heat, the range of 50-200 degreeC is preferable, More preferably, it is the range of 80-150 degreeC, As the heating time, the range of 1 second-10 hours is preferable, More preferably, it is 10 seconds-1 hour Heating in a range.

  Among the light irradiation treatments, vacuum ultraviolet (VUV light) treatment is more preferable.

  For example, it is preferable to perform conversion treatment by applying a vacuum ultraviolet ray after applying and drying a perhydropolysilazane coating solution on a substrate. This vacuum ultraviolet irradiation breaks the molecular bond of polysilazane, and even a small amount of oxygen in the film or atmosphere can be efficiently converted into ozone or active oxygen. Silica modification) is promoted, and the resulting ceramic film becomes denser. VUV light irradiation is effective at any time point after the coating film is formed.

  The vacuum ultraviolet ray in the present invention is specifically a vacuum ultraviolet ray of 100 to 200 nm. The irradiation intensity and / or irradiation time of vacuum ultraviolet rays can be set as appropriate. As the vacuum ultraviolet irradiation apparatus, a commercially available lamp (for example, manufactured by USHIO INC.) Can be used.

  VUV light irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be coated. For example, in the case of batch processing, a precursor coating film such as a silazane compound can be processed in a vacuum ultraviolet ray baking furnace equipped with a vacuum ultraviolet ray generation source. The vacuum ultraviolet baking furnace itself is generally known, and for example, Ushio Electric Co., Ltd. can be used. Further, when the support provided with the coating film of the silazane compound is in the form of a long film, it is continuously irradiated with vacuum ultraviolet rays in the drying zone provided with the vacuum ultraviolet ray generation source as described above while being transported. As a result, the surface can be ceramicized.

  Since the vacuum ultraviolet light is larger than the interatomic bonding force of most substances, it can be preferably used because the bonding of atoms can be cut directly by the action of only photons called photon processes. By using this action, the reforming process can be efficiently performed at a low temperature without requiring hydrolysis.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

Since noble gas atoms such as Xe, Kr, Ar, Ne, and the like are chemically bonded and do not form molecules, they are called inert gases. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon, e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric) in a similar very thin discharge called micro discharge, the electric charge accumulates on the dielectric surface, and the micro discharge disappears. The dielectric barrier discharge is a discharge in which this micro discharge spreads over the entire tube wall and is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge can be used in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp, the electrodes, and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through in order to extract light to the outside in order to discharge in the entire discharge space. Must. For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are arranged in close contact, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space only by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As for the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. If the curved surface is mirrored with aluminum, it becomes a light reflector.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. Yes.

  Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light with a long wavelength that causes a temperature increase due to light is not emitted and energy is irradiated with a short wavelength in the ultraviolet region, the surface temperature of the irradiation object can be suppressed from increasing.

  Moreover, if the irradiation intensity of vacuum ultraviolet rays is high, the probability that a photon and a chemical bond in polysilazane will collide increases, and the modification reaction can be shortened. Further, since the number of photons penetrating to the inside increases, the modified film thickness can be increased and / or the film quality can be improved (densification). However, if the irradiation time is too long, the planarity may be deteriorated and other materials of the gas barrier member may be damaged. In general, the progress of the reaction is considered by the integrated light quantity expressed by the product of the irradiation intensity and the irradiation time. The absolute value may be important.

Therefore, in the present invention, in the VUV irradiation step, it is preferable to perform a modification treatment that gives a maximum irradiation intensity of 100 to 200 mW / cm ² at least once. This is because the reforming efficiency increases when the reforming treatment is performed with the strength.

  The irradiation time of VUV light can be arbitrarily set, but the irradiation time in the high illuminance process is preferably 0.1 second to 3 minutes. More preferably, it is 0.5 second to 1 minute.

  The oxygen concentration at the time of VUV light irradiation is preferably 100 to 10,000 ppm (1%). More preferably, it is 100-5000 ppm. If the oxygen concentration is higher than the above-mentioned concentration range, the reforming efficiency is lowered. If the oxygen concentration is lower than the above-mentioned range, the replacement time with the atmosphere becomes longer, and at the same time, continuous production such as roll-to-roll is performed. When performing, the amount of air (including oxygen) entrained in the VUV irradiation chamber by web conveyance increases, and the oxygen concentration cannot be adjusted unless a large flow rate of gas is allowed to flow.

  In the polysilazane-containing coating film, oxygen and a small amount of water are mixed at the time of application, and there are also adsorbed oxygen and adsorbed water in the thin glass and resin layers other than the polysilazane-containing coating film. Even if not introduced, it has been found that there are sufficient oxygen sources for supplying oxygen required for the reforming reaction. Further, as described above, the 172 nm VUV light is absorbed by oxygen, and the amount of 172 nm light reaching the film surface is reduced, thereby reducing the efficiency of the light treatment. That is, at the time of VUV light irradiation, it is preferable to perform the modification treatment in a state where the VUV light efficiently reaches the coating film in a state where the oxygen concentration is as low as possible.

  As the gas other than oxygen at the time of VUV light irradiation, a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

<Material that reacts with water>
In the present invention, a gas barrier film having a gas barrier layer containing a metal oxide is brought into contact with the surface of the gas barrier layer with a material that reacts with water in an environment where the absolute humidity is 0.001 to ³ g / m ^3. .

  If the gas barrier layer is an ideal metal oxide film, a permeation gas, that is, a low molecule such as water vapor, does not dissolve or diffuse, so that a complete gas barrier ability should be exhibited. However, in practice, it is very difficult to obtain the desired gas barrier property because it is impossible to suppress the occurrence of defects such as cracks and pinholes in the film formation process.

  The present invention discloses a process technique for selectively repairing such defects in the metal oxide film. Specifically, while trapping water by inducing moisture diffusing in the gas barrier layer to the surface through cracks, pinholes, etc., and bringing it into contact with a material that reacts with water in a low humidity environment In other words, this is a technique for filling defects.

  The material that reacts with water in the present invention is not particularly limited as long as it reacts with water and adheres to defects in the gas barrier layer. However, in order to fill the defects in the gas barrier layer, it reacts with water and solidifies (crystallizes). ) Or a material that polymerizes (crosslinks) is preferable, and a material that forms a molecular bond with the side surface of the defect and can also repair defects more densely by crosslinking the material itself. preferable.

  Specific materials include silane compounds, silazane compounds, titanium compounds, zirconium compounds or cyanoacrylates known as the main components of instant adhesives, which are commonly used as surface treatment agents and oxide film raw materials. it can.

  Examples of the silane compound include chlorosilane, alkylsilane, and alkoxysilane. Examples of the silazane compound include low-molecular silazane and polysilazane. Silane compounds can be classified into a monofunctional type, a bifunctional type, and a trifunctional type based on the difference in the number of substitutions of leaving groups (chloro groups, alkyl groups, alkoxy groups) with silicon atoms. In addition to general surface treatment agents having alkyl groups, fluorinated alkyl groups, aryl groups, etc. as substituents other than leaving groups, various functional functional groups (for example, vinyl groups, epoxy groups, styryl). Various materials substituted with a group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, an isocyanate group, etc. are also available.

  Examples of titanium compounds include organic titanium alkoxides, organic titanium acylates, and organic titanium chelates. Examples of zirconium compounds include organic zirconium alkoxides, organic zirconium acylates, and organic zirconium chelates. Is available as

  In addition, cyanoacrylate reacts instantaneously with a small amount of moisture and polymerizes (hardens), and thus is used as a main component of an instantaneous adhesive. Examples of cyanoacrylate include methyl cyanoacrylate, ethyl cyanoacrylate, methoxyethyl cyanoacrylate, butyl cyanoacrylate, and octyl cyanoacrylate.

  The material that reacts with water in the present invention is a material that forms a metal oxide having an O—M—O bond (where M represents Si, Ti, Al, Zr, or Mg) by hydrolysis. It is more preferable in that a defect can be expected to be repaired more densely by forming a molecular bond with the side surface of the defect and also cross-linking the material itself. Specific examples include silane compounds, silazane compounds, titanium compounds, and zirconium compounds as described above.

[Defect repair process]
FIG. 4 is a schematic sectional view showing a defect repairing process of the gas barrier film of the present invention.

  The gas barrier film 20 in which the gas barrier layer 22 is provided on the resin base material 21 cannot avoid the presence of defects 31 such as cracks and pinholes in the gas barrier layer 22 after production (FIG. 4 ( 1)).

When the gas barrier film 20 having the defect 31 is placed in a humid environment 41 (for example, an environment having an absolute humidity of 5 to 120 g / m ³ ), moisture that has entered from the resin substrate side is interfaced with the gas barrier layer. It remains diffused in the vicinity (FIG. 4 (2)). If the intruding moisture is removed by baking or the like, extra steps are added. Further, when an electronic device or the like is sealed as it is, a crack is spread from the defect at the time of bending due to the remaining defect, which causes deterioration of bending resistance.

In the present invention, the gas barrier film 20 having defects 31 is brought into contact with the surface of the gas barrier layer 22 with the material 34 that reacts with water in an environment 41 without humidity (an environment where the absolute humidity is 0.001 to ³ g / m ³ ). By this, water diffused in the gas barrier layer, the undercoating layer such as the stress relaxation layer, the flattening layer, etc., the base material, etc. reacts with the material 34 that reacts with water through the defects in the gas barrier layer, and hydrolyzed The defect 31 is repaired (repair location 32) by forming a metal oxide or the like (FIGS. 4 (3) and (4)).

  Furthermore, the defect repair process of the present invention will be described in more detail.

<Low humidity environment>
In the present invention, a gas barrier film having a gas barrier layer containing a metal oxide is brought into contact with the surface of the gas barrier layer with a material that reacts with water in an environment where the absolute humidity is 0.001 to ³ g / m ^3. .

  A selective defect repair effect can be aimed at by bringing the material that reacts with water into contact with the surface of the gas barrier layer in such a low humidity environment.

Here, absolute humidity (also referred to as volume absolute humidity) g / m ³ is the mass (g) of water vapor contained in a unit volume (1 m ³ ) of gas.

In the present invention, the absolute humidity in the environment when the material that reacts with water is brought into contact with the surface of the gas barrier layer containing the metal oxide is set to 0.001 to ³ g / m ³ . By placing the gas barrier film in such a low-humidity environment, the gas barrier layer, the undercoating layer such as the stress relaxation layer / flattening layer, and the water diffusing in the base material are cracked or pinned in the gas barrier layer. Since it is induced to the surface through a hole, it is considered that selective reaction at a defective portion becomes possible by contacting the material that reacts with water in a low-humidity environment.

  In order to obtain the low-humidity environment of the present invention, the inside of the reaction system may be adjusted to a dry gas atmosphere or a reduced pressure.

For example, if the inside of the reaction system is replaced with dry gas, it is possible to easily adjust the absolute humidity within the range of the present invention. The gas used in the dry gas atmosphere is not particularly limited as long as there is no reactivity with the material that reacts with water, and examples thereof include air, N ₂ , and rare gases such as He, Ne, Ar, Kr, and Xe. However, air and N ₂ are preferable in terms of cost.

  In order to reduce the environment, it can be easily adjusted by using a general vacuum pump such as a rotary pump.

The absolute humidity in the low humidity environment of the present invention are in the range of 0.001~3g / ^{m 3} in order to create a 0.001 g / ^{m 3} less environment, more prolonged treatment, or higher This is because a vacuum is required, resulting in a decrease in productivity and an increase in cost. Further, when the absolute humidity exceeds ³ g / m ³ , the water vapor contained in the environment reacts with the material that reacts with water first, or the water vapor is adsorbed on the entire gas barrier film surface, so that the selective portion in the defective portion is selectively treated. This is because it is not a reaction and an efficient repair effect cannot be expected.

  As a method for setting a low humidity environment, the temperature and relative humidity in the system may be adjusted so as to be within the range of the absolute humidity of the present invention.

For example, when the temperature when the system is filled with dry air under atmospheric pressure is 25 ° C. and the relative humidity is 1% RH, the absolute humidity is 0.2 g / m ³ . In order to obtain the absolute humidity from the temperature and relative humidity, the following calculation formula may be used.

Absolute humidity (g / m ³ ) = Relative humidity (%) / 100 × 0.794e ⁻² × EXP (−6096.9385 / T + 21.209642−2.711193e ⁻² × T + 1.6739552e ⁻⁵ × T ² +2. 433352 × LN (T)) / (1 + 0.00366 × (T-273.15))
(Wherein, T is absolute temperature (K) = 273.15 + t (° C.))
Also, for example, the absolute humidity of the atmosphere at a temperature of 20 ° C. and a relative humidity of 30% RH is 5 g / m ^{3, and} therefore the absolute humidity in the system when the pressure in the sealed system filled with the atmosphere is reduced to 0.01 atm. In the present invention, it can be determined to be 0.05 g / m ³ .

Thus, the absolute humidity of the humidity environment of the present invention is adjusted to 0.001~3g / ^{m 3,} it is preferable to be 0.001 to 1 g / ^{m 3} in terms of more efficient defect repair can be expected, More preferably, it is the range of 0.001-0.2 g / m < ³ >.

  Further, the temperature and humidity in the system when adjusting the absolute humidity within this range are not particularly limited as long as they are possible, but the temperature is −10 ° C. to 200 ° C., and the relative humidity is 0.01% RH to 30%. It is preferable to be within the range of about% RH in consideration of the resistance and productivity of the substrate, and the temperature is within a range of about 20 ° C. to 150 ° C. and a relative humidity of about 0.01% RH to 15% RH. More preferred. The dew point is preferably within a range of about -80 ° C to 0 ° C.

  On the other hand, the atmospheric pressure for obtaining a low-humidity environment under reduced pressure is preferably set to about 0.001 atm to about 0.1 atm from the viewpoint of production suitability and cost.

<Method of processing materials that react with water>
In the present invention, examples of a method for treating a material that reacts with water in a low-humidity environment include a gas phase process and a liquid phase process.

  Specifically, in a state where the gas barrier film of the present invention is held in a low-humidity environment, the gas barrier film of the present invention can be used under a low-humidity environment such as a gas phase process method such as exposure to vapor of a material that reacts with water. Liquid phase process methods such as removing material by evaporating or washing in a low-humidity environment after immersion or application in a material that reacts with water, or a solution in which the material is dissolved in a dehydrating solvent, etc. Can be mentioned.

  Specific methods for maintaining the inside of the reaction system in a low-humidity environment include a method using a dry air supply device, a method using a device such as a glow box that can be replaced with an inert gas such as nitrogen, and a vacuum oven. The method used, etc. are mentioned.

  The substrate temperature and material liquid temperature when the material that reacts with water reacts with the defective part of the gas barrier film may remain at the set low humidity environment atmosphere, but for the purpose of promoting the reaction, a hot plate, a sheet heater, etc. May be used to heat the substrate, or when the film is immersed in the material solution, the material solution may be heated to an appropriate temperature. The heating temperature is preferably 40 ° C. to 200 ° C., more preferably 60 ° C. to 150 ° C., although it varies depending on the heat resistant temperature of the substrate or the boiling point of the solvent for diluting the material.

<Environment including humidity>
In the production of a gas barrier film, as described in Patent Document 6, it is common to carry out under vacuum until the final step, but in the present invention, in an environment where the absolute humidity is 0.001 to ³ g / m ³ , Before bringing the material that reacts with the surface of the gas barrier layer into contact with the gas barrier layer, the gas barrier film is preferably exposed to an environment having an absolute humidity of 5 to 120 g / m ³ .

Thus, before the absolute humidity of contacting a material which reacts with water in gas barrier layer surface in an environment of low humidity 0.001~3g / ^{m 3,} the absolute humidity includes a humidity 5~120g / ^{m 3} By exposing the gas barrier film to the environment, the amount of water contained in the gas barrier film increases, so that the reaction with the material that reacts with water in the defective part further proceeds, and a greater repair effect can be expected. preferable.

As the environment including humidity in the present invention, the absolute humidity is preferably in the range of 5 to 120 g / m ³ , but the absolute humidity in a general atmospheric atmosphere is more preferably in the range of 5 to 20 g / m ³ . Even if it is a gas barrier film produced under a low humidity environment or a vacuum environment by exposing the gas barrier film to an environment containing a humidity of 5 to 20 g / m ^{3 in} absolute humidity, the repair effect of the present invention It is possible to include a sufficient amount of water in the film to obtain In this case, the exposure time in the air atmosphere is considered to be about 1 to 2 to 3 months, but about 2 to 3 to 2 to 3 weeks is sufficient.

As a specific method for obtaining an environment including humidity according to the present invention, a normal air atmosphere as described above is sufficient, but in order to obtain a higher humidity environment where the absolute humidity is 20 to 120 g / m ^3. For example, a method using a high-temperature and high-humidity oven that can be set to 60 ° C. and 90% RH is convenient. In this case, the time of exposure to high temperature and high humidity is about 2 to 3 seconds to 2 to 3 hours, and if it is exposed for a longer time, it contains too much water, so before the repair process in a low humidity environment Since a separate drying process is required, it is rather counterproductive.

<Energy provision>
In the present invention, when the gas barrier film is brought into contact with the surface of the gas barrier layer with a material that reacts with water in an environment where the absolute humidity is 0.001 to ³ g / m ³ , the gas barrier layer It is preferable to impart energy to the.

  The energy applied to the gas barrier layer may be thermal energy, light energy, microwave energy, or the like, but the present invention is not limited to these, and promotes the reaction of water with a material that reacts with water. Any energy is acceptable. However, in the repair process of the present invention, since there are many cases in which the dehydration condensation reaction is finally performed and the reaction is completed, it is very effective to apply heat energy.

  Specific energy application methods include, for example, a method of applying thermal energy by a hot plate, a sheet heater, an infrared heater, an oven, hot air, etc., and an optical energy such as ultraviolet rays by a UV ozone device, an excimer lamp, an excimer laser, or the like. And a method of applying microwave energy by a microwave generator.

<Support>
Next, the support body in this invention is demonstrated.

  The support in the present invention is preferably a plastic film because it can be applied to mass production such as roll-to-roll, is easy to handle, and can be manufactured at low cost.

  Examples of the plastic film include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE ), Polypropylene (PP), Polystyrene (PS), Nylon (Ny), Aromatic polyamide, Polyetheretherketone, Polysulfone, Polyethersulfone, Polyimide, Polyetherimide, and other resin films, Sil with organic-inorganic hybrid structure A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having sesquioxane as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin can be used. .

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the gas barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used.

  The thickness of the support according to the present invention is preferably in the range of 5 to 500 μm, more preferably in the range of 25 to 250 μm.

  The support according to the present invention is preferably transparent. Since the support is transparent and the layer formed on the support is also transparent, it becomes possible to make a transparent gas barrier film, so it can also be used as a transparent substrate such as a photoelectric conversion element (solar cell). Because it becomes.

  Here, that the support is transparent means that the light transmittance of visible light (400 to 700 nm) is 80% or more.

  Moreover, the unstretched film may be sufficient as the plastic film using the resin etc. which were mentioned above, and a stretched film may be sufficient as it.

  The plastic film support used in the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

  Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  Moreover, in the plastic film which concerns on this invention, you may give a corona treatment before forming an organic layer or an inorganic layer.

  Moreover, you may form an anchor-coat agent layer on the support body in this invention in order to improve the adhesiveness with respect to the support body surface of the layer to form.

  Examples of the anchor coating agent used in this anchor coating agent layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination.

  Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to.

The application amount of the anchor coating agent is preferably about 0.1 g / m ^{2 to} 5 g / m ² (dry state).

  In the present invention, a stress relaxation layer for relaxing stress applied to the gas barrier layer between the support including the anchor coating agent layer and the gas barrier layer or between the gas barrier layers, and a smooth layer for smoothing the surface of the resin support It is preferable to provide a bleed-out preventing layer for preventing bleed-out from the resin support. Below, a stress relaxation layer, a smooth layer, and a bleed-out prevention layer are demonstrated.

(Stress relaxation layer)
When a gas barrier layer containing a metal oxide is formed on a resin support as in the present invention, there is a large difference in physical properties such as an elastic modulus, a thermal contraction rate, and a thermal expansion coefficient. The larger the value is, the more stress is concentrated on the gas barrier layer, which may cause problems such as cracks and film peeling. In addition, there is a concern that cracks may occur due to bending stress received during handling or film conveyance.

  Therefore, for example, a stress relaxation layer having a physical property value such as hardness, density, or elastic modulus located between the resin support and the gas barrier layer is provided between the resin support and the gas barrier layer, or the gas barrier layer is formed as a thick film. It is considered that there is an effect of suppressing the occurrence of cracks or the like by providing a stress relaxation layer between the gas barrier layers for the purpose of achieving the above.

  Specifically, it is possible to form the stress relaxation layer from an acrylic resin containing silica particles used for a smooth layer, which will be described later, or a silazane compound or a siloxane compound that is also used to form a gas barrier layer. is there.

  For example, when designing the stress relaxation layer so that the density is lower than that of the upper gas barrier layer, even if the same material as the gas barrier layer is used, the degree of conversion reaction can be selected by selecting the conversion method and conversion conditions, or the layer to be provided. It is possible to control by appropriately selecting the film thickness and the like. It is also possible to control the obtained film density itself by selecting the material used for the stress relaxation layer.

  As a specific material, for example, organopolysilazane, perhydropolysilazane, alkoxysilane, or a mixture thereof is preferably used.

  In particular, when a mixture of organopolysilazane such as methylhydropolysilazane and perhydropolysilazane is used as the stress relaxation layer, and perhydropolysilazane is used for the gas barrier layer, the physical property value such as hardness, density or elastic modulus should be given a gradient. It is preferable in that it can have a function of relieving stress against bending of the barrier film and can improve the adhesion between the stress relaxation layer and the gas barrier layer.

  The mixing ratio of the organopolysilazane and perhydropolysilazane may be appropriately selected for the purpose of controlling the desired physical property value, and is not particularly limited. For example, when the ratio of organopolysilazane is high, the density can be set low, and when the ratio of perhydropolysilazane is high, the density can be set high.

  In addition to the resin support and the gas barrier layer, for example, when a plurality of gas barrier layers are provided, the stress relaxation layer may be alternately provided between the gas barrier layers, and the external stress is relieved. For the purpose, it may be provided in the uppermost layer of the gas barrier film. For the stress relaxation layer, it is preferable to select a material configuration or a layer configuration that does not cause cracks or local adhesion failure at the layer interface with heat, humidity, and time.

(Smooth layer)
The smooth layer on the support flattens the rough surface of the transparent resin film support on which protrusions and the like exist, or fills irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions on the transparent resin film support. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive resin.

  As the photosensitive resin of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  The composition of the photosensitive resin may contain a photopolymerization initiator.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing pinholes from being generated in the film.

  The smoothness of the smooth layer is a value expressed by surface roughness, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When the value is smaller than this range, the coating property is impaired when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or a wireless bar at the stage of coating a silicon compound described later. There is a case. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured by an AFM (Atomic Force Microscope) with a detector having a stylus having a minimum tip radius, and the measurement direction is several tens by the stylus having a minimum tip radius. It is the roughness related to the amplitude of fine irregularities measured in a section of μm many times.

(Additive to smooth layer)
One preferred embodiment includes reactive silica particles (hereinafter also simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin.

  Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be.

  Moreover, as a photosensitive resin, what adjusted solid content by mixing a general purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle size of the reactive silica particles is preferably 0.001 μm to 0.1 μm. By making the average particle diameter in such a range, by using it in combination with a matting agent composed of inorganic particles having an average particle diameter of 1 μm to 10 μm, which will be described later, optical properties satisfying a good balance between anti-glare properties and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties.

  Further, it is more preferable to use an average particle size of 0.001 μm to 0.01 μm.

  Improves adhesion between the smooth layer and the gas barrier layer, prevents bending of the base material, prevents cracks when heat-treated, and provides optical properties such as transparency and refractive index of the gas barrier film From the viewpoint of maintaining good physical properties, the smooth layer preferably contains the inorganic particles as described above in a mass ratio of 20% to 60%.

  In the present invention, the polymerizable unsaturated group-modified hydrolyzable silane compound is chemically bonded to the silica particles by generating a silyloxy group by a hydrolysis reaction of the hydrolyzable silyl group. Can be used as reactive silica particles.

  Examples of the hydrolyzable silyl group include a carboxylylated silyl group such as an alkoxysilyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oximesilyl group, and a hydridosilyl group.

  Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.

  As the thickness of the smooth layer used in the present invention, the smoothness of the support is improved, and the balance of the optical properties of the support is easily adjusted, and the smooth layer is provided only on one surface of the support. From the viewpoint of preventing curling of the smooth film in the case, the range of 1 μm to 10 μm is preferable, and the range of 2 μm to 7 μm is more preferable.

(Bleed-out prevention layer)
The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the film support to the surface and contaminate the contact surface. Provided on the opposite side of the support having a layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And monounsaturated organic compounds having one polymerizable unsaturated group.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 μm to 5 μm are preferable.

  As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the bleed-out prevention layer. It is desirable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure.

  In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer improves the heat resistance of the support, makes it easier to adjust the balance of the optical properties of the support, and the bleed-out prevention layer is provided only on one side of the substrate. From the viewpoint of preventing the support from curling, a range of 1 to 10 μm is preferable, and a range of 2 to 7 μm is more preferable.

<Use of gas barrier film>
The gas barrier film of the present invention can be used as various sealing materials and substrates.

  The gas barrier film of the present invention can be particularly useful for organic electronic devices such as organic photoelectric conversion elements and organic electroluminescence elements. For example, when used in a photoelectric conversion element, the gas barrier film of the present invention is transparent, so that the gas barrier film can be used as a substrate to receive sunlight from this side. That is, on the gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a substrate for a photoelectric conversion element.

  Then, the ITO transparent conductive film provided on the substrate can be used as an electrode, a semiconductor layer can be provided thereon, and an electrode made of a metal film can be formed to form a photoelectric conversion element. Another sealing material may be stacked on top of this (although it may be the same), and the gas barrier film substrate and the surroundings are adhered to each other, and the photoelectric conversion element can be sealed by enclosing the element. The influence of the gas such as oxygen on the photoelectric conversion element can be sealed.

  The base material for photoelectric conversion elements is obtained by producing a transparent conductive film on the gas barrier film of the present invention.

  The transparent conductive film can be formed by using a vacuum deposition method, a sputtering method, or the like, or by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin. In addition, as a film thickness of a transparent conductive film, the transparent conductive film of the range of 0.1-1000 nm is preferable.

  Subsequently, the organic photoelectric conversion element which is one of the preferable uses of the gas barrier film of this invention is demonstrated.

<Organic photoelectric conversion element>
(Sealing substrate and manufacturing method thereof)
In the gas barrier film of the present invention, a transparent conductive film is further formed on the gas barrier film, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are laminated on the transparent conductive film. Further, another gas barrier film can be used as a sealing base material, and sealing can be performed by repeated adhesion.

  As another sealing material (sealing substrate) to be used, the gas barrier film of the present invention can be used. In addition, for example, a known gas barrier film used for packaging materials, such as a plastic film deposited with silicon oxide or aluminum oxide, a dense ceramic layer, and a flexible impact relaxation polymer layer are alternately laminated. A gas barrier film having the structure described above can be used as the sealing film.

  In particular, a resin-laminated (polymer film) metal foil cannot be used as a gas barrier film on the light extraction side, but it is a low-cost, low moisture-permeable sealing material and does not intend to extract light (with transparency). When not required), it is preferable as a sealing film.

  In the present invention, the metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .

  As metal foil, there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil. Among these various metal foils, a particularly preferred metal foil is an Al foil.

  The thickness of the metal foil is 6 from the viewpoints of preventing pinholes during use due to the material used for the metal foil, improving gas barrier properties (moisture permeability, oxygen permeability), and improving productivity. It is preferable to adjust to a range of ˜50 μm.

  In the metal foil laminated with a resin film (polymer film), as the resin film, various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene Resin, polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, Examples thereof include vinylidene chloride resins.

  Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. In addition, a polyethylene resin having a low density or a high density can be used.

  As will be described later, as a method for sealing the two films, for example, a method of laminating a commonly used impulse sealer heat-fusible resin layer, fusing with an impulse sealer, and sealing is preferable. Further, the sealing between the gas barrier films is preferably 300 μm or less from the viewpoint of improving the handling property of the film at the time of sealing work and enabling easy thermal fusion with an impulse sealer or the like.

(Sealing of organic photoelectric conversion elements)
In the organic photoelectric conversion element of the present invention, after forming each layer constituting the organic photoelectric conversion element on the organic photoelectric conversion element substrate obtained by forming the transparent conductive film on the gas barrier film of the present invention, Using the above sealing substrate, the organic photoelectric conversion element can be sealed so as to cover the cathode surface with the sealing substrate in an environment purged with an inert gas.

As the inert gas, a rare gas such as He and Ar is preferably used in addition to N ₂ , but a rare gas in which He and Ar are mixed is also preferable, and the ratio of the inert gas in the gas is 90 to 99.99. It is preferably 9% by volume. Preservability is improved by sealing in an environment purged with an inert gas.

  In addition, when sealing the organic photoelectric conversion element using the metal foil laminated with the resin film (polymer film), a ceramic layer is formed on the metal foil instead of the laminated resin film surface, The ceramic layer surface is preferably bonded to the cathode of the organic photoelectric conversion element.

  When the polymer film surface of the sealing film is bonded to the cathode of the organic photoelectric conversion element, conduction may occur partially.

  As a sealing method for bonding the sealing film to the cathode of the organic photoelectric conversion element, a resin film that can be fused with a commonly used impulse sealer, for example, ethylene vinyl acetate copolymer (EVA), polypropylene (PP) film, polyethylene ( There is a method in which a heat-fusible film such as a PE) film is laminated and fused and sealed with an impulse sealer.

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm.

  However, if the amount of adhesive applied is too large, tunneling, seepage, shrinkage, etc. may occur, so the amount of adhesive is preferably adjusted to 3-5 μm in dry film thickness. It is preferable to do.

  Hot melt lamination is a method in which a hot melt adhesive is melted and an adhesive layer is applied to a support, and the thickness of the adhesive layer is generally a method that can be set in a wide range of 1 to 50 μm. Commonly used base resins for hot melt adhesives include EVA, EEA, polyethylene, butyl rubber, etc., rosin, xylene resin, terpene resin, styrene resin, etc. as tackifiers, wax etc. It is added as an agent.

  The extrusion laminating method is a method in which a resin melted at a high temperature is coated on a support with a die, and the thickness of the resin layer can generally be set in a wide range of 10 to 50 μm.

  In general, LDPE, EVA, PP or the like is used as the resin used for the extrusion laminate.

  Next, the constituent layers of the organic photoelectric conversion element of the present invention will be described.

(Configuration of organic photoelectric conversion element)
Although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to these.

  There is no restriction | limiting in particular as a structure of the organic photoelectric conversion element of this invention, The electric power generation layer (The layer where the p-type semiconductor and the n-type semiconductor were mixed, a bulk heterojunction layer, and i layer is also sandwiched between the anode and the cathode. ) Is at least one layer and is preferably an element that generates current when irradiated with light.

  The preferable specific example of the layer structure of an organic photoelectric conversion element is shown below.

(I) Anode / power generation layer (also referred to as photoelectric conversion layer) / cathode (ii) Anode / hole transport layer / power generation layer (photoelectric conversion layer) / cathode (iii) Anode / hole transport layer / power generation layer (photoelectric conversion) Layer) / electron transport layer / cathode (iv) anode / hole transport layer / p-type semiconductor layer / power generation layer (photoelectric conversion layer) / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / First power generation layer (also referred to as photoelectric conversion layer) / electron transport layer / intermediate electrode / hole transport layer / second power generation layer (also referred to as photoelectric conversion layer) / electron transport layer / cathode.

(Power generation layer (also called photoelectric conversion layer))
The power generation layer of the organic photoelectric conversion element of the present invention will be described.

  The power generation layer of the organic photoelectric conversion element of the present invention needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons, and these are substantially two layers and heterojunction layers. May be formed, or a bulk heterojunction layer in a mixed state in one layer may be formed, but the bulk heterojunction layer has a more preferable configuration from the viewpoint of improving photoelectric conversion efficiency. is there.

  A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like the light emitting layer of the organic EL device, the power generation layer of the organic photoelectric conversion device of the present invention sandwiches the power generation layer between the hole transport layer and the electron transport layer, thereby extracting the holes and electrons into the anode / cathode. Therefore, the configurations ((ii) and (iii)) having them are preferably used.

  Further, in order to improve the rectification of holes and electrons (selection of carrier extraction), the power generation layer itself is sandwiched between layers of a p-type semiconductor material and a single n-type semiconductor material as shown in (iv). A configuration (also referred to as a pin configuration) may be used.

  Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

  Instead of the sandwich structure in the organic photoelectric conversion element 10 shown in FIG. 1 for the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), a hole transport layer 14 and an electron transport layer 16 are respectively formed on a pair of comb-like electrodes. A back contact type organic photoelectric conversion element in which the photoelectric conversion unit 15 is disposed thereon can be configured.

  Furthermore, the preferable aspect of the organic photoelectric conversion element which concerns on detailed this invention is demonstrated using FIGS. 1-3.

  FIG. 1 is a cross-sectional view showing an example of a solar cell composed of a bulk heterojunction organic photoelectric conversion element. In FIG. 1, a bulk heterojunction organic photoelectric conversion element 10 has an anode 12, a hole transport layer 17, a power generation layer 14 of a bulk heterojunction layer, an electron transport layer 18, and a cathode 13 sequentially stacked on one surface of a substrate 11. Has been.

  The substrate 11 is a member that holds the anode 12, the power generation layer 14, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member.

  As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction organic photoelectric conversion element 10 may be configured by forming the anode 12 and the cathode 13 on both surfaces of the power generation layer 14.

  The power generation layer 14 is a layer that converts light energy into electrical energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material relatively functions as an electron donor (donor), and the n-type semiconductor material relatively functions as an electron acceptor (acceptor).

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed.

  The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes.

  For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13.

  If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  Although not shown in FIG. 1, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.

  As a more preferable configuration, the power generation layer 14 has a so-called p-i-n three-layer configuration (FIG. 2). A normal bulk heterojunction layer is a single i layer in which a p-type semiconductor material and an n-type semiconductor layer are mixed. By sandwiching between a p-layer composed of a single p-type semiconductor material and an n-layer composed of a single n-type semiconductor material, Further, the rectification property of holes and electrons is further increased, loss due to recombination of charge-separated holes and electrons is reduced, and higher photoelectric conversion efficiency can be obtained.

  Furthermore, it is good also as a tandem-type structure which laminated | stacked such a photoelectric conversion element for the purpose of the improvement of sunlight utilization factor (photoelectric conversion efficiency).

  FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first power generation layer 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second power generation layer 16, and then the counter electrode 13 are stacked. By stacking, a tandem structure can be obtained. The second power generation layer 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first power generation layer 14 ′ or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. Further, both the first power generation layer 14 ′ and the second power generation layer 16 may have the above-described three-layer structure of pin.

(P-type semiconductor material, n-type semiconductor material)
The material used for formation of the electric power generation layer (it is also called a photoelectric converting layer) of the organic photoelectric conversion element of this invention is demonstrated.

(P-type semiconductor material)
Examples of the p-type semiconductor material used for forming the bulk heterojunction layer preferably used as the power generation layer of the organic photoelectric conversion device of the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zesulene, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, circobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above condensed polycycle include International Publication No. 03/16599, International Publication No. 03/28125, US Pat. No. 6,690,029, Japanese Patent Application Laid-Open No. 2004-107216. A pentacene derivative having a substituent as described in U.S. Pat. No. 2003/136964, J. Pat. Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  As the conjugated polymer, for example, a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, a polythiophene-thienothiophene copolymer described in p328, a polythiophene-diketopyrrolopyrrole copolymer described in WO08 / 000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

  In addition, oligomeric materials instead of polymer materials include thiophene hexamer α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, a compound that is highly soluble in an organic solvent to the extent that a solution process can be performed and that can form a crystalline thin film after drying to achieve high mobility is preferable.

  In addition, when the electron transport layer is formed on the power generation layer by coating, there is a problem that the electron transport layer solution dissolves the power generation layer. Therefore, a material that can be insolubilized after coating by a solution process may be used. .

  Examples of such materials include materials that can be insolubilized by polymerizing the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or by applying energy such as heat as described in US Patent Application Publication No. 2003/136964 and JP-A-2008-16834, etc., the soluble substituent reacts to insolubilize ( And materials).

(N-type semiconductor material)
The n-type semiconductor material used for the bulk heterojunction layer according to the present invention is not particularly limited. For example, a perfluoro compound (perfluoropentacene or the like) in which a hydrogen atom of a p-type semiconductor such as fullerene or octaazaporphyrin is substituted with a fluorine atom. Perfluorophthalocyanine, etc.), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides, and polymers containing such imidized compounds as a skeleton A compound etc. can be mentioned.

  However, fullerene derivatives that can perform charge separation efficiently with various p-type semiconductor materials at high speed (up to 50 fs) are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), etc. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61- Butyric acid-isobutyl ester (PCBiB), [6,6] -phenyl C61-butyric acid-n-hexyl ester (PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes such as JP-A 2006-199674, metallocene fullerenes such as JP-A 2008-130889, US Pat. No. 7,329,709, etc. It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as fullerene having a cyclic ether group such as a calligraphy.

(Hole transport layer, electron block layer)
In the organic photoelectric conversion element 10 of the present invention, the hole transport layer 17 can be taken out between the bulk heterojunction layer and the anode, and charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable to have.

  As a material constituting these layers, for example, as the hole transport layer 17, PEDOT such as Product name BaytronP manufactured by Stark Vitec, polyaniline and its doped material, described in WO 06/19270, etc. Cyanide compounds can be used.

  Note that the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer has a rectifying effect that prevents electrons generated in the bulk heterojunction layer from flowing to the anode side. The electronic block function is provided.

  Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used.

  A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

(Electron transport layer / hole blocking layer)
In the organic photoelectric conversion element 10 of the present invention, by forming the electron transport layer 18 between the bulk heterojunction layer and the cathode, it becomes possible to more efficiently take out the charges generated in the bulk heterojunction layer. It is preferable to have these layers.

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, or the like) can be used. Similarly, a p-type semiconductor material used for a bulk heterojunction layer is used. The electron transport layer having a HOMO level deeper than the HOMO level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side.

  Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.

  Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.

  A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

(Other layers)
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

(Transparent electrode (first electrode))
In the transparent electrode according to the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element configuration, but preferably the transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires, and carbon nanotubes can be used.

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

(Counter electrode (second electrode))
The counter electrode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used.

Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The counter electrode can be produced by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  If a metal material is used as the conductive material of the counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer, and more photoelectric conversion is performed. Efficiency is improved and preferable.

  Further, the counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a nanowire, or a nanostructure. A dispersion is preferable because a transparent and highly conductive counter electrode can be formed by a coating method.

  Moreover, when making the counter electrode side light-transmitting, for example, after forming a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound in a thin film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

(Intermediate electrode)
In addition, the material of the intermediate electrode required in the case of the tandem configuration as in (v) (or FIG. 3) is preferably a layer using a compound having both transparency and conductivity. (Such as ITO, AZO, FTO, transparent metal oxides such as titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, PEDOT: PSS, polyaniline, etc. Or the like can be used.

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating. Is preferable.

(Metal nanowires)
As the conductive fiber according to the present invention, an organic fiber or inorganic fiber coated with a metal, a conductive metal oxide fiber, a metal nanowire, a carbon fiber, a carbon nanotube, or the like can be used, and a metal nanowire is preferable.

  In general, a metal nanowire refers to a linear structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a linear structure having a diameter of nm size.

  The metal nanowire according to the present invention preferably has an average length of 3 μm or more in order to form a long conductive path with a single metal nanowire and to exhibit appropriate light scattering properties. 3-500 micrometers is preferable and it is especially preferable that it is 3-300 micrometers. In addition, the relative standard deviation of the length is preferably 40% or less.

  Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity.

  In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used.

  For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871.

  In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in an aqueous system, and since the conductivity of silver is the highest among metals, the method for producing metal nanowires used in the present invention Can be preferably applied.

  In the present invention, the metal nanowires come into contact with each other to form a three-dimensional conductive network, exhibiting high conductivity, and allowing light to pass through the window of the conductive network where no metal nanowire exists. In addition, the power generation from the organic power generation layer can be efficiently performed by the scattering effect of the metal nanowires. If a metal nanowire is installed in the 1st electrode at the side close | similar to an organic electric power generation layer part, since this scattering effect can be utilized more effectively, it is more preferable embodiment.

(Optical function layer)
The organic photoelectric conversion element according to the present invention may have various optical function layers for the purpose of more efficient light reception of sunlight. As the optical functional layer, for example, a light condensing layer such as an antireflection layer or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved.

  The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  Examples of the light diffusion layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

(Film formation method / surface treatment method)
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed, and a transport layer / electrode include a vapor deposition method and a coating method (including a cast method and a spin coat method). Among these, examples of the method for forming the bulk heterojunction layer include a vapor deposition method and a coating method (including a casting method and a spin coating method).

  Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. Also, the coating method is excellent in production speed.

  Although there is no restriction | limiting in the coating method used in this case, For example, a spin coat method, the cast method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

  After application, it is preferable to perform heating in order to cause removal of residual solvent, moisture, and gas and increase mobility and absorption longwave by crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The power generation layer (bulk heterojunction layer) 14 may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, it can be formed by using a material that can be insolubilized after coating as described above.

(Patterning)
The method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be subjected to mask vapor deposition during vacuum deposition or patterned by a known method such as etching or lift-off. Alternatively, the pattern may be formed by transferring a pattern formed on another substrate.

  Therefore, the following measurements were performed in order to confirm the inclination characteristics of the wire and the presence of the copper-zinc-nickel ternary alloy plating layer.

  Measurement by XPS (X-ray photoelectron microscopy) The element distribution (concentration gradient) in the depth direction of the copper-zinc-nickel ternary plated wire was investigated before and after the final wet drawing using this apparatus. This device repeats the routine of measuring the element concentration on the measurement surface of the sample, scraping the sample surface with Ar gas, and measuring the element concentration on the new surface of the sample surface that has been formed by cutting, in the depth direction of the sample. The concentration gradient of the element is analyzed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.

Example 1
<< Production of gas barrier film >>
<Preparation of gas barrier film 1>
(Support)
As a support, a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Films, Ltd.) with easy-adhesion processing on both sides is annealed at 170 ° C. for 30 minutes, and then a smooth layer is formed on the surface of the polyester film. The one provided with a bleed-out prevention layer on the back side was used.

(Formation of smooth layer)
On the surface side of the polyester film, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied and applied with a wire bar so that the film thickness after drying was 4 μm. After drying for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing was performed at a curing condition of 1.0 J / cm ² to form a smooth layer (clear hard coat layer: CHC layer).

(Formation of bleed-out prevention layer)
On the back side of the polyester film, UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation was applied, and after applying with a wire bar so that the film thickness after drying was 4 μm, curing conditions: 1.0 J / Cm ² , using a high-pressure mercury lamp under air, drying conditions; curing was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer.

(Formation of silica precursor layer)
On this support, a 20% by mass dibutyl ether solution of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20, amine catalyst type) and a 20% by mass dibutyl ether solution of perhydropolysilazane (AZ Electronic Materials). By using a solution prepared by mixing a 1: 4 mass ratio of Aquamica NN120-20 (manufactured by Co., Ltd.) with spin coating (5000 rpm, 60 seconds) and then drying at 80 ° C. for 1 minute. A silica precursor layer was formed.

(Formation of gas barrier layer)
Further, excimer lamp irradiation (excimer light intensity: 130 mW / cm ² (172 nm)), excimer light source lamp and substrate using stage movable xenon excimer irradiation device (MECL-M-1-200, manufactured by MD Excimer) Distance: 3 mm, stage temperature: 100 ° C., processing environment: dry nitrogen atmosphere, oxygen concentration in the processing environment: 0.1%, transported 10 times at a stage moving speed of 10 mm / sec), so that at least the film surface is A gas barrier layer (300 nm) converted to silica (silicon dioxide) was formed on the support.

  Here, the film thickness was confirmed by a cross-sectional photograph of a TEM (Transmission Electron Microscope), and the film composition in the film thickness direction could be confirmed by a combination of sputtering and XPS surface analysis.

  The XPS surface analyzer used for the surface analysis is not particularly limited, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  Further, the presence of OH groups on the film surface could be confirmed by combining the sputtering method and Tof-SIMS (Time-Of-Flight Secondary Ion Spectrometry).

Subsequently, the gas barrier film provided with the gas barrier layer of the present invention containing silicon dioxide as a metal oxide was stored for one day in an environment of 23 ° C. and 23% RH. The absolute humidity at this time was determined to be 4.7 g / m ³ .

(Defect repair)
Next, the inside of the reaction system was maintained in a low-humidity environment so that the dew point was −60 ° C. (temperature 25 ° C.) using a dry air supply device (DA Series, manufactured by Airpro Corporation). The absolute humidity at this time was determined to be 0.01 g / m ³ . In the reaction system maintained in this low humidity environment, a 2% by weight acetone solution of ethyl cyanoacrylate was dip coated on the gas barrier film, washed with acetone, and then dried in a low humidity environment for 1 hour. A gas barrier film 1 was prepared.

<Preparation of gas barrier film 2>
In the production of the gas barrier film 1, the gas barrier film provided with the gas barrier layer was placed in an oven maintained at 60 ° C. and 95% RH (absolute humidity: 123 g / m ³ ) for 1 minute, and then ethyl cyano in a low humidity environment. A gas barrier film 2 of the present invention was produced in the same manner except that it was reacted with acrylate.

<Preparation of gas barrier film 3>
In the production of the gas barrier film 1, the gas barrier film provided with the gas barrier layer was stored for one day in an environment of 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ), and then in a low humidity environment. A gas barrier film 3 of the present invention was produced in the same manner except that it was reacted with cyanoacrylate.

<Preparation of gas barrier film 4>
In the production of the gas barrier film 1, the gas barrier film provided with the gas barrier layer was stored for one day in an environment of 25 ° C. and 25% RH (absolute humidity: 5.8 g / m ³ ), and then in a low humidity environment. A gas barrier film 4 of the present invention was produced in the same manner except that it was reacted with cyanoacrylate.

<Preparation of gas barrier film 5>
In the production of the gas barrier film 1, the gas barrier film provided with the gas barrier layer was placed in an oven maintained at 60 ° C. and 90% RH (absolute humidity: 117 g / m ³ ) for 1 minute, and then ethyl cyano in a low humidity environment. A gas barrier film 5 of the present invention was produced in the same manner except that it was reacted with acrylate.

<Preparation of gas barrier film 6>
In the production of the gas barrier film 3, a gas barrier film 6 was produced in the same manner except that tetraethoxysilane vapor was used instead of ethyl cyanoacrylate reacted in a low-humidity environment.

  Next, in a system maintained in a low-humidity environment, the vessel containing tetraethoxysilane is heated at a boiling point (168 ° C.) or lower to slowly generate tetraethoxysilane vapor, and the gas barrier layer side receives the vapor. The gas barrier film was installed in this manner, reacted with tetraethoxysilane for 10 minutes, washed with acetone, and then dried in a low-humidity environment for 1 hour to produce the gas barrier film 6 of the present invention.

<Preparation of gas barrier film 7>
The gas barrier film 6 was produced in the same manner except that it was carried out in a system in which the environment for reacting the tetraethoxysilane vapor was adjusted to 20 ° C. and 15% RH (absolute humidity: 2.6 g / m ³ ). A gas barrier film 7 was prepared.

<Preparation of gas barrier film 8>
In the production of the gas barrier film 6, the gas barrier film was similarly used except that trichloromethylsilane was used instead of tetraethoxysilane to be reacted in a low-humidity environment, and it was further heated on a hot plate at 120 ° C. after the treatment. 8 was produced.

  Next, in a reaction system maintained in a low-humidity environment, a 2% by weight toluene solution of trichloromethylsilane was applied on the gas barrier film of the present invention by dip coating, washed with toluene and acetone, air-dried in a low-humidity environment, Furthermore, the gas barrier film 8 of this invention was produced by heating at 120 degreeC on a hotplate for 10 minutes.

<Preparation of gas barrier film 9>
In the production of the gas barrier film 8, perhydropolysilazane is used in place of trichloromethylsilane that is reacted in a low-humidity environment, and an ultraviolet ray is irradiated by an excimer lamp as an additional energy to be applied. The gas barrier film 9 of the present invention was produced in the same manner except that the film was transported twice.

<Preparation of gas barrier film 10>
In the production of the gas barrier film 8, the inside of the system is placed in a dry nitrogen atmosphere as a low-humidity environment, and dip coating is performed using titanium tetraisopropoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS TA-10) instead of trichloromethylsilane. After cleaning, the gas barrier property of the present invention was the same except that the gas barrier film was heated in a vacuum oven under reduced pressure (absolute humidity: 0.005 g / m ³ ) at 120 ° C. for 10 minutes to give additional energy. Film 10 was produced.

<Preparation of gas barrier film 11>
In the production of the gas barrier film 10, the gas barrier film 11 of the present invention was similarly obtained except that zirconium tetranormal propoxide (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS ZA-40) was used instead of titanium tetraisopropoxide. Was made.

<Preparation of gas barrier film 12>
A 125 μm thick polyester film provided with a smooth layer on the front side and a bleed-out prevention layer on the back side was used as the support.

  A silicon dioxide film is formed on the support by an atmospheric pressure plasma CVD method (with introduction of oxygen gas, using tetraethoxysilane as a raw material gas, and adjusting a raw material gas supply amount and energy output density at a base material temperature of 100 ° C.) Was formed to 200 nm.

Subsequently, the gas barrier film provided with the gas barrier layer of the present invention containing silicon dioxide was stored for 1 day in an environment of 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ).

Next, the gas barrier film 12 of the present invention was produced by reacting the vapor of tetraethoxysilane and the surface of the gas barrier layer for 10 minutes at 100 ° C. in a dry nitrogen atmosphere (absolute humidity: 0.3 g / m ³ ). .

<Preparation of gas barrier film 13>
In the production of the gas barrier film 12, a gas barrier film in which a silicon dioxide film is formed by a vacuum plasma CVD method instead of an atmospheric pressure plasma CVD method is used in an environment of 25 ° C. and 60% RH (absolute humidity: 13.8 g / m ³ ). After being stored for 1 day in a dry nitrogen atmosphere, the substrate is immersed in a 2% by weight toluene solution of hexamethyldisilazane heated to 60 ° C. for 10 minutes, washed and air dried, and then heated to 120 ° C. on a hot plate. The gas barrier film of the present invention was similarly prepared except that the gas barrier film was finally heated in a vacuum oven under reduced pressure (absolute humidity: 0.001 g / m ³ ) at 120 ° C. for 1 hour. Film 13 was produced.

<Preparation of gas barrier film 14>
In the production of the gas barrier film 7, the comparison was performed in the same manner except that it was performed in a system in which the environment for reacting the vapor of tetraethoxysilane was adjusted to 20 ° C. and 20% RH (absolute humidity: 3.5 g / m ³ ). A gas barrier film 14 was produced.

<Preparation of gas barrier film 15>
In the production of the gas barrier film 13, a gas barrier layer made of an ITO film is formed by a sputtering method, and an aluminum oxide is obtained in a dry nitrogen atmosphere with reference to the method described in Patent Document 6 (WO2008 / 57045 pamphlet). A comparative gas barrier film 15 was produced by providing a particle layer.

<Preparation of gas barrier film 16>
In the production of the gas barrier film 3, the gas barrier film in which the gas barrier layer containing silicon dioxide was formed by the conversion treatment of the perhydropolysilazane coating film was placed in an environment of 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ). This is the same except that after 3 days storage at 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ), a 3% ethanol aqueous solution of tetraethoxysilane was dip-coated and then air-dried. Thus, a comparative gas barrier film 16 was produced.

<Preparation of gas barrier film 17>
In the production of the gas barrier film 13, the gas barrier film in which the silicon dioxide film was formed by the vacuum plasma CVD method was stored for one day in an environment of 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ). A comparative gas barrier film 17 was produced in the same manner except that the repair process of the invention was not performed.

<Preparation of gas barrier film 18>
In the same manner as the production of the gas barrier film 3, a gas barrier film in which a gas barrier layer containing silicon dioxide was formed by conversion treatment of a perhydropolysilazane coating film was 25 ° C. and 40% RH (absolute humidity: 9.2 g / m ³ ). A comparative gas barrier film 18 was prepared in the same manner except that the repair process of the present invention was not performed after storage for 1 day in the environment.

<< Evaluation of gas barrier film >>
The obtained gas barrier film was immediately subjected to wet thermo (60 ° C., 90% RH) treatment and then evaluated for gas barrier properties (water vapor permeability) after bending as described below.

<Evaluation of gas barrier properties>
The water vapor permeability (WVTR (g / m ² / day)) was measured as follows as an index of gas barrier properties.

(Bending treatment)
The gas barrier film was repeatedly bent 50 times at an angle of 180 degrees so that the surface of the gas barrier layer of the gas barrier film was on the outside and the curvature of the gas barrier film was 20 mmφ.

(apparatus)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Production of evaluation cell)
On the gas barrier layer surface of the gas barrier film, a vacuum vapor deposition device (JEOL vacuum vapor deposition device JEE-400) is used to mask other than the portion where the transparent conductive film is to be deposited (12 mm x 12 mm is 9 locations), and metal calcium is deposited. I let you.

  Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained gas barrier film with both sides sealed is stored under high temperature and high humidity of 60 ° C. and 90% RH, and based on the method (calcium method) described in JP-A-2005-283561, the corrosion amount of metallic calcium The amount of moisture permeated into the cell was calculated.

  In addition, in order to confirm that there is no permeation of water vapor other than from the surface of the gas barrier layer of the gas barrier film, metal calcium is deposited using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film as a comparative sample. The obtained samples were stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no metallic calcium corrosion occurred even after 2000 hours.

The manufacturing method of the produced gas barrier film is shown in Table 1, and the measured water vapor transmission rate (WVTR (g / m ² / day)) is shown in Table 2.

  As shown in Tables 1 and 2, the gas barrier films 1 to 13 of the present invention all have high gas barrier properties, and the water vapor transmission rate is deteriorated after the wet thermo (60 ° C., 90% RH) treatment and after the bending treatment. Was found to be small.

  On the other hand, it can be seen that the comparative films 14 to 18 do not have a high gas barrier property, and after the wet thermo treatment, the gas barrier property is greatly deteriorated after the bending treatment, and the stability is lower than that of the present invention. I understood.

Example 2
Using the gas barrier film produced in Example 1, a gas barrier film having the following transparent conductive film was produced. Subsequently, the organic photoelectric conversion element was produced using the gas barrier film which has a transparent conductive film.

<< Production of gas barrier film having transparent conductive film >>
As the plasma discharge apparatus, a parallel plate type electrode is used, and the gas barrier film subjected to forced deterioration produced in Example 1 is placed between the electrodes, and a mixed gas is introduced to form a thin film. It was.

  In addition, as a ground (ground) electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried. The electrode was cured by ultraviolet irradiation and sealed, and the dielectric surface coated in this way was polished, smoothed, and processed to have an Rmax of 5 μm.

  Further, as the application electrode, an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space.

Moreover, as a power source used for plasma generation, a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm ² of power was supplied at a frequency of 13.56 MHz.

  A mixed gas having the following composition is allowed to flow between the electrodes to form a plasma state, the gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film is formed to a thickness of 150 nm on each gas barrier layer. Thus, a gas barrier film with a transparent conductive film was produced.

(Plasma generation conditions)
Discharge gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
<< Production of organic photoelectric conversion element >>
A gas barrier film having the obtained transparent conductive film (150 nm, sheet resistance 10 Ω / □) was patterned to a width of 2 mm using a photolithography technique and wet etching to form a first electrode.

  The pattern-formed first electrode (anode) is cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried with nitrogen blow, and finally cleaned with ultraviolet ozone. A transparent substrate was obtained.

  On the surface of the obtained transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, is applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to transport holes. Layers were formed.

  Thereafter, each transparent substrate was brought into a nitrogen chamber and produced in a nitrogen atmosphere.

  First, the substrate was heat-treated at 150 ° C. for 10 minutes in a nitrogen atmosphere. Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Co., Ltd .: 6,6-phenyl-C61-butyric acid methyl ester) are added to chlorobenzene at 3.0% by mass. A liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm, while being filtered through a filter, and allowed to dry at room temperature. Subsequently, heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

Next, the transparent substrate on which the series of functional layers has been formed is moved into the vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then the deposition rate is 0.01 nm / second. Laminate lithium fluoride at 0.6 nm, and then, through a 2 mm wide shadow mask (deposit the light receiving part so as to be 2 × 2 mm and deposit), deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec. Thus, a second electrode (cathode) was formed.

  The obtained organic photoelectric conversion element was moved to a nitrogen chamber and sealed using the following sealing film and UV curable resin to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), an epoxy-based photocurable adhesive as a sealing material with the gas barrier layer side of the same two gas barrier films used for the substrate facing inside Was applied to the gas barrier layer, and the organic photoelectric conversion element was sandwiched and adhered between the gas barrier films, and then cured by irradiating UV light from one side of the substrate. Thus, an organic photoelectric conversion element sealed on both sides was obtained.

<< Evaluation of organic photoelectric conversion element >>
(Durability evaluation)
About the produced photoelectric conversion element, the light of the intensity | strength of 100 mW / cm < ² > of a solar simulator (AM1.5G filter) is irradiated, the mask which made the effective area 4.0mm < ² > is piled up on a light-receiving part, and IV characteristic is evaluated. Thus, the short-circuit current density Jsc (mA / cm ² ), the open-circuit voltage Voc (V), and the fill factor FF (%) are respectively measured at the four light receiving portions formed on the same element, and obtained according to the following formula 1. The four-point average value of the energy conversion efficiency PCE (%) was calculated.

(Formula 1)
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial battery characteristics was measured, and the degree of deterioration with time in the conversion efficiency remaining rate after the accelerated test was stored for 1000 hours in a temperature of 60 ° C. and a humidity of 90% RH (conversion efficiency / initial conversion efficiency × 100 (%)), the following criteria were used for evaluation.

◎: 80% or more ◎: 70% or more, less than 80% ○: 40% or more, less than 70% Δ: 20% or more, less than 40% ×: less than 20% Table 3 shows the evaluation results.

  From Table 3, it was found that the organic photoelectric conversion element of the present invention was extremely superior in durability as compared with the comparative organic photoelectric conversion element.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Anode 13 Cathode 14 Power generation layer (bulk heterojunction layer)
14pp layer 14i i layer 14n n layer 14 'first power generation layer 15 charge recombination layer 16 second power generation layer 17 hole transport layer 18 electron transport layer 20 organic photoelectric conversion element 21 resin base material 22 barrier layer 31 defect 32 Collection point 33 Water 34 Material that reacts with water 41 Humid environment 42 Humid environment

Claims (7)

In the method for producing a gas barrier film having a gas barrier layer containing a metal oxide, the gas barrier film is brought into contact with the surface of the gas barrier layer with a material that reacts with water in an environment where the absolute humidity is 0.001 to ³ g / m ^3. A method for producing a gas barrier film, characterized by comprising: 2. The gas barrier film according to claim 1, wherein the gas barrier film is exposed to an environment having an absolute humidity of 5 to 120 g / m ³ before the material that reacts with water contacts the surface of the gas barrier layer. Manufacturing method.   The method for producing a gas barrier film according to claim 1 or 2, wherein the material that reacts with water forms a metal oxide having an O-M-O bond by hydrolysis. However, M represents Si, Ti, Al, Zr or Mg.   The method for producing a gas barrier film according to claim 3, wherein the metal oxide has a hydroxyl group.   The energy is imparted to the gas barrier layer when the material that reacts with water is brought into contact with the surface of the gas barrier layer or after the material is brought into contact with the water. The manufacturing method of the gas-barrier film of description.   A gas barrier film produced by the method for producing a gas barrier film according to claim 1.   An organic electronic device sealed with the gas barrier film according to claim 6.

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