JP2012116101A - Method of manufacturing gas barrier film, and gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a gas barrier film having the roll-to-roll production suitability and excellent in gas barrier performance.SOLUTION: The method of manufacturing the gas barrier film has at least one layer of gas barrier layer, wherein a coating film is manufactured by applying a solution containing an organic precursor compound on a resin substrate 1 conveyed with a tension impressed thereto and reformation is performed by irradiating the coating film with a vacuum ultraviolet ray by means of an excimer lamp 2. The surface temperature of the excimer lamp is 150°C or below and the shortest distance between the surface of the excimer lamp and the resin substrate is 10 mm or less. The method of manufacturing the gas barrier film satisfies following relation [1]: 0.3≤B/A≤4.0, wherein a thickness of the resin substrate is denoted by A (μm) and a tension per m width in the irradiation of the vacuum ultraviolet ray is denoted by B(N).

Description

  The present invention relates to a method for producing a gas barrier film and a gas barrier film produced by the production method. More specifically, the present invention relates to a method for producing a gas barrier film mainly used in a package such as an electronic device, or an organic electroluminescence (EL) element, a solar cell element, a liquid crystal display element, and the like, and a gas barrier film produced by the production method. .

  Conventionally, a gas barrier film in which a plurality of layers including a thin film of a metal oxide such as aluminum oxide, magnesium oxide, and silicon oxide are laminated on the surface of a plastic substrate or film needs to block various gases such as water vapor and oxygen. It is widely used for packaging of articles to be used, packaging for preventing deterioration of foods, industrial products and pharmaceuticals. In addition to packaging applications, they are used in solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, and the like.

  As a method for forming such a gas barrier film, a chemical deposition method (plasma CVD method) in which an organic silicon compound typified by tetraethoxysilane (TEOS) is used to form a film on a substrate while being oxidized with oxygen plasma under reduced pressure. (Chemical Vapor Deposition) or a semiconductor laser is used to evaporate metal Si and deposit it on a substrate in the presence of oxygen.

Since these methods can form a thin film with an accurate composition on a substrate, they have been preferably used for the formation of metal oxide thin films including SiO _2. It took a lot of time, the continuous production was difficult, the equipment was enlarged, and the productivity was remarkably bad.

  In order to solve such problems, for the purpose of improving productivity, a silicon-containing compound is applied, a method of forming a silicon oxide thin film by modifying the coating film, and plasma is generated under atmospheric pressure even in the same CVD method. Attempts have been made to form films under atmospheric pressure, and gas barrier films are also being studied.

  As a silicon oxide film that can be generally produced by a solution process, a technique of forming an alkoxide compound as a raw material by a method called a sol-gel method is known. This sol-gel method generally requires heating to a high temperature, and further, a large volume shrinkage occurs in the course of the dehydration condensation reaction, resulting in a large number of defects in the film.

  In order to prevent this, methods have been found to mix organic substances that are not directly involved in the formation of oxides into the raw material solution. However, these organic substances remain in the film, and there is a concern that the barrier properties of the entire film may deteriorate. Has been. For these reasons, it has been difficult to directly use an oxide film produced by a sol-gel method as a protective film of a flexible electronic device.

  As another method, it has been proposed to form a silicon oxide film using a silazane compound having a basic structure of silazane structure (Si—N) as a raw material. The reaction in this case is not a dehydration condensation polymerization but a direct substitution reaction from nitrogen to oxygen, so that the mass yield before and after the reaction is large from 80% to 100% or more, and there are few defects in the film due to volume shrinkage. It is known that films can be obtained.

  However, the formation of the silicon oxide film by the substitution reaction of the silazane compound requires a high temperature of 450 ° C. or higher, and cannot be applied to a flexible substrate such as plastic.

  As a means for solving such a problem, a method of forming a silicon oxide film by applying vacuum ultraviolet light to a coating film formed from a silazane compound solution has been proposed. Only photons called photon processes are used to bond atoms using light energy of 100 to 200 nm called vacuum ultraviolet rays (hereinafter also referred to as “VUV” or “VUV light”), which is larger than the interatomic bonding force in silazane compounds. By the action of, a silicon oxide film can be formed at a relatively low temperature by allowing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.

  Further, from the viewpoint of production of a gas barrier film, it is necessary industrially to be able to produce continuously by so-called roll-to-roll.

  As a roll-to-roll manufacturing method, a method of manufacturing a gas barrier film by conveying a film at a speed of about 1 m / min or 10 m / min and irradiating an excimer lamp on a silazane compound coating film is known. (See Patent Document 1 and Non-Patent Document 1).

  However, these methods also have problems such as insufficient production stability and insufficient barrier performance of the produced gas barrier film.

Special table 2009-503157

Leibniz Institute of Surface Modification Biological Report 2008/2009: P18-P21

  The present invention has been made in view of the above-mentioned problems and situations, and its solution is a gas barrier property that has a production suitability for a roll-to-roll method and can produce a gas barrier film having excellent gas barrier performance. It is providing the manufacturing method of a film, and the gas-barrier film obtained by it.

  The above-mentioned problem according to the present invention is solved by the following means.

1. A coating film is prepared by applying a solution containing an inorganic precursor compound onto a resin substrate conveyed while applying tension, and the coating film is modified by irradiating it with vacuum ultraviolet rays using an excimer lamp. In the method for producing a gas barrier film having at least one gas barrier layer formed by quality treatment,
The surface temperature of the excimer lamp is 150 ° C. or less, and the shortest distance between the excimer lamp surface and the resin substrate is 10 mm or less,
A gas barrier film satisfying the following equation [1], where A (μm) is the thickness of the resin substrate, and B (N) is the tension per m width when the vacuum ultraviolet ray is irradiated. Manufacturing method.

0.3 ≦ B / A ≦ 4.0... [1]
2. 2. The method for producing a gas barrier film according to 1 above, wherein the resin base material is conveyed in a free span in the step of modifying.

  3. 3. The method for producing a gas barrier film as described in 1 or 2 above, wherein perhydropolysilazane is used as the inorganic precursor compound.

  4). A gas barrier film produced by the method for producing a gas barrier film according to any one of 1 to 3 above.

  By the above means of the present invention, it is possible to provide a method for producing a gas barrier film having extremely high gas barrier performance and having a roll-to-roll system production suitability, and a gas barrier film produced by the production method.

It is the figure which carried out the free span conveyance of the resin base material to the perpendicular direction, and showed the modification | reformation process process by a vacuum ultraviolet irradiation device typically. It is the figure which showed typically the cross-sectional structure of the horizontal direction of an excimer lamp. It is the figure which showed typically the cross-section of the lamp | ramp longitudinal direction of the excimer lamp which has a water cooling mechanism.

The method for producing a gas barrier film according to the present invention comprises: applying a solution containing an inorganic precursor compound on a resin substrate that is conveyed while applying a tension to produce a coating film; In the method for producing a gas barrier film having at least one gas barrier layer formed by reforming by irradiating with vacuum ultraviolet rays using
The excimer lamp surface temperature is 150 ° C. or less, and the shortest distance between the lamp surface and the resin substrate is 10 mm or less,
Furthermore, when the thickness of the resin base material is A (μm) and the tension per m width upon irradiation with vacuum ultraviolet rays is B (N), the gas barrier property satisfies the following formula [1] It is a manufacturing method of a film.

0.3 ≦ B / A ≦ 4.0... [1]
In addition, the method for producing a gas barrier film of the present invention is a method for producing a gas barrier film in which the resin base material is preferably subjected to free span conveyance in the step of modifying treatment by irradiation with vacuum ultraviolet rays. According to the production method of the present invention, it is possible to obtain a stable gas barrier property even when the resin base material is subjected to free span conveyance, and the degree of freedom in designing the production line is increased, so that the initial investment can be suppressed. It has many merits.

  Furthermore, in the method for producing a gas barrier film of the present invention, it is preferable to use perhydropolysilazane as the inorganic precursor compound.

  Furthermore, the gas barrier film of the present invention is a gas barrier film produced by any one of the production methods described above.

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

<< Gas barrier film and method for producing the same >>
The gas barrier layer according to the present invention is formed by applying a solution containing an inorganic precursor compound on a resin substrate, and then modifying the coating film containing the inorganic precursor compound by a method of irradiating vacuum ultraviolet rays. A part of the film is modified into an inorganic film such as metal oxide, metal nitride, or metal oxynitride to form a gas barrier layer.

  Here, the modification treatment in the present invention means that a part of the coating film is modified into an inorganic film by irradiating the coating film containing the inorganic precursor compound with vacuum ultraviolet rays.

  Since the vacuum ultraviolet light is larger than the interatomic bonding force of most substances, it is possible to directly break the atomic bond by the action of only photons called photon processes, and the inorganic precursor compound coating film can be efficiently inorganic. It becomes possible to modify the film.

  Irradiation with vacuum ultraviolet rays is effective at any time after the formation of the coating film.

(Vacuum ultraviolet irradiation device with excimer lamp)
Specifically, a rare gas excimer lamp that emits vacuum ultraviolet rays of 100 to 200 nm is preferably used in the vacuum ultraviolet irradiation device according to the present invention.

Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded to form no molecule, they are called inert gases. However, noble gas atoms (excited atoms) that have gained energy by discharge can combine with other atoms to form molecules. When the rare gas is xenon,
e + Xe → Xe ^*
Xe * + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
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. Moreover, since extra light is not radiated | emitted, the temperature of a target object can be kept comparatively low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  As a light source for efficiently irradiating the excimer light, there is a dielectric barrier discharge lamp. The lamp is configured to cause discharge between electrodes via a dielectric. Generally, it is sufficient that at least one electrode is disposed outside a discharge vessel made of a dielectric. As the lamp, for example, a rare gas such as xenon is enclosed in a double cylindrical discharge vessel composed of a thick tube and a thin tube made of quartz glass, and a net-like first electrode is provided outside the discharge vessel. Some have another electrode provided inside the inner tube. In the lamp, a dielectric barrier discharge is generated inside the discharge vessel by applying a high-frequency voltage between the electrodes, and excimer light is generated when excimer molecules such as xenon generated by the discharge dissociate.

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

  However, the quartz glass tube itself of the lamp is heated by the lamp lighting, and the lamp tube surface temperature may reach 200 ° C. or more within a few minutes from the lighting, and the distance between the lamp tube surface is close to the irradiation object. In this case, for example, when the thickness is 10 mm or less, the temperature of the irradiation object rises due to the radiant heat of the lamp tube surface.

  As in the present invention, a layer formed on a resin substrate is conveyed while applying tension by a roll-to-roll method, and the resin substrate being conveyed is irradiated with vacuum ultraviolet rays using an excimer lamp. In a manufacturing method having a treatment step, the resin base material temperature rises due to the influence of the temperature of the excimer lamp tube surface during the modification treatment step.

  Since the resin base material generally used has Tg around 100 ° C., it has temperature dependency of the elastic modulus, and when the temperature exceeds Tg, the elastic modulus rapidly decreases. When the temperature of the resin base material rises while transporting while applying a constant tension by the roll-to-roll method, the elongation of the resin base material increases as the elastic modulus decreases. For example, when the resin substrate temperature is increased from 25 ° C. to 130 ° C., the elongation of the resin substrate can be 3 to 4 times.

  On the other hand, in the present invention, in the above-described modification treatment step, at least a part of the coating film containing the inorganic precursor compound is modified into an inorganic coating film. At this time, the inorganic precursor compound has an elastic modulus. Is low and the breaking elongation is large, whereas the inorganic coating film modified with this has a high elastic modulus and a small breaking elongation. This means that when the resin substrate temperature is greatly increased in the modification treatment step and the elongation of the resin substrate is greatly increased during the modification treatment step, the modified inorganic coating film is in the resin substrate. This means that there is an increased concern that cracks will not occur following the elongation of the material, and that an inorganic coating film with cracks will greatly degrade the gas barrier properties. In addition, the elongation of the resin base material may not be constant in the width direction, and when the tension is removed and the temperature is returned to room temperature, the resin base material may be unevenly deformed, which may greatly deteriorate the quality of the gas barrier film. is there. These are problems that appear more prominently at the conveyance site in the free span.

  Here, the conveyance part in the free span means a part other than the part where the base material is wound around the conveyance roll or the conveyance belt and is in contact with the conveyance roll or the conveyance belt. The term “substrate” means that the base material is transported without contacting the transport roll or the transport belt.

  If the distance between the lamp tube surface and the object to be irradiated is increased, the temperature rise of the object to be irradiated can be suppressed. However, the illuminance of vacuum ultraviolet rays on the surface of the object to be irradiated decreases and the modification efficiency by irradiation also decreases. As a result, the gas barrier property is deteriorated as a result, or the productivity is lowered, for example, the line speed is lowered.

  In this way, a reforming process is carried out to form a gas barrier layer by modifying the inorganic precursor compound coating film formed on the resin substrate conveyed while being applied with tension in a roll-to-roll system by vacuum ultraviolet irradiation. In the treatment process, process management at a level that has not been considered in the past is necessary for improving the gas barrier performance and productivity, and the present inventor has arrived at the present invention as a result of earnest examination.

  In the modification treatment step of the present invention, the surface temperature of the excimer lamp used in the vacuum ultraviolet irradiation apparatus is 150 ° C. or lower. The surface temperature of the excimer lamp is more preferably 80 ° C. or higher and 130 ° C. or lower.

  When the surface temperature of the excimer lamp exceeds 150 ° C., the gas barrier property of the resin base material is greatly deteriorated, and there is a concern that the base material is deformed. Moreover, since it becomes more stable and favorable gas-barrier property will be obtained by setting it as 130 degrees C or less, it is preferable. Furthermore, it is preferable to set the temperature to 80 ° C. or higher because the temperature difference of the heat generating part with respect to the cooling part of the entire quartz glass tube of the excimer lamp can be reduced and lamp deterioration such as crack generation can be suppressed.

  In the present invention, the shortest distance between the surface of the excimer lamp and the resin base material is 10 mm or less. Among these, Preferably they are 3 mm or more and 5 mm or less.

  Here, the surface of the excimer lamp means the surface of the portion closest to the resin base material in the quartz glass tube surface of the excimer lamp. If there is a translucent shield such as a quartz glass plate (other than gas) between the excimer lamp's quartz glass tube surface and the resin base, the resin base is the most transparent surface of the translucent shield. It means the surface of the near part. The surface temperature of the excimer lamp can be measured with a thermocouple type, thermistor type contact thermometer, radiation thermometer, or the like.

  The excimer lamp tube surface temperature can be controlled by directly adjusting the temperature of the lamp using a gas or liquid refrigerant or by cooling the lamp holder to indirectly adjust the temperature of the lamp. Specifically, JP 04-301357, JP 09-274893, JP 11-329365, JP 2000-030667, JP 2000-106147, JP 2000-331649, JP 2001-126666, JP 2001. -185089, JP 2001-267280, JP 2002-042736, JP 2002-191965, JP 2002-203520, JP 2002-263596, JP 2003-115281, JP 2003-167100, JP 2004-265770. , JP-A-2007-128661, JP-A-2008-084568, JP-A-2008-147058, and JP-A-2009-043599 can be used.

  Further, the quartz glass tube of the excimer lamp has a characteristic that the transmittance of 172 nm light decreases as the temperature rises, and controlling the excimer lamp tube surface temperature within the temperature range of the present invention is a practical output of the lamp. This contributes to improving reforming efficiency and gas barrier properties.

(Oxygen concentration during vacuum ultraviolet irradiation)
The oxygen concentration during vacuum ultraviolet irradiation according to the present invention is preferably 10 to 10,000 ppm (1%), and more preferably 50 to 5000 ppm.

  When irradiation with vacuum ultraviolet rays is performed in an atmosphere containing a large amount (a few percent level) of oxygen gas, the gas barrier film after the reforming process has an excessive oxygen structure, and the gas barrier properties deteriorate.

  Further, as described above, 172 nm vacuum ultraviolet rays are absorbed by oxygen and the amount of light at 172 nm reaching the film surface is reduced, so that the processing efficiency by light is likely to be lowered.

  It is preferable to use a dry inert gas as a gas other than oxygen during irradiation with vacuum ultraviolet rays, and it is particularly preferable to use a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of oxygen gas and inert gas introduced into the chamber of the vacuum ultraviolet irradiation apparatus and changing the flow rate ratio.

  Here, the temperature of the resin base material during the modification treatment can be adjusted by heating or cooling the gas introduced into the chamber and spraying the gas onto the irradiation surface side or the back surface side of the resin base material.

<< Resin base material: Support body >>
The resin base material (also referred to as “support”) of the gas barrier film of the present invention has a gas barrier property (also simply referred to as “barrier film”) having a gas barrier property (also simply referred to as “barrier property”) described later. As long as it is formed of an organic material capable of holding the same, there is no particular limitation.

  For example, acrylic ester, methacrylic 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, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films, and silsesquioxane having an organic-inorganic hybrid structure Examples thereof include a heat-resistant transparent film having a skeleton (product name: Sila-DEC, manufactured by Chisso Corporation), and a resin film formed by laminating two or more layers of the resin.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), etc. are preferably used, and optical transparency, heat resistance, inorganic layer, gas barrier, etc. In terms of adhesion to the adhesive layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. Among these, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are more preferable in terms of breaking strength and cost, and polyethylene terephthalate (PET) is most preferable in terms of remarkable improvement in gas barrier properties and cost in the present invention. .

  The thickness of the support is preferably 10 μm to 500 μm, more preferably 20 to 250 μm, and still more preferably 30 to 150 μm. When the thickness of the support is in the range of 10 μm to 500 μm, a stable gas barrier property can be obtained, and it is suitable for roll-to-roll conveyance.

  In the present invention, when the thickness of the resin base material is A (μm) and the tension per m width upon irradiation with vacuum ultraviolet rays is B (N), it is necessary to satisfy the following formula [1]. .

0.3 ≦ B / A ≦ 4.0... [1]
When the formula “B / A” exceeds 4.0, there is a concern that cracks may occur in the barrier layer during the modification treatment. On the other hand, if it is less than 0.3, the tension between the rolls of the resin base material becomes insufficient, and the flatness at the time of the modification treatment cannot be maintained, and there is a concern that the modification unevenness occurs.

  A more preferable range of the formula “B / A” is 0.3 or more and 2.7 or less.

  An excimer lamp surface temperature and the shortest distance between the lamp surface and the resin base material are controlled within the range of the present invention, and the numerical value of the formula [1] is maintained within this range, thereby providing a more stable and favorable gas barrier. It was found that the property can be obtained with high productivity.

  Here, the thickness A (μm) of the resin base material is a thickness including these constituent layers when an anchor coat agent layer, a smooth layer, etc., which will be described later, are provided.

  Further, the thickness of the resin base material can be measured by a transmission electron microscope (TEM) or the like. Specifically, it can be measured by measuring the thickness of the resin substrate measured by a transmission electron microscope at 10 or more locations and obtaining the average value.

  Moreover, the tension per m width at the time of irradiation with vacuum ultraviolet rays can be applied to the resin substrate with a constant tension by a tension adjusting mechanism.

  Moreover, it is preferable that the resin base material (support body) which concerns on this invention is transparent.

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

  Since the resin base material (support) is transparent and the layer formed on the resin base material is also transparent, a transparent gas barrier film can be obtained. Thus, a transparent substrate such as an organic EL element is obtained. It is also possible.

  Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it.

  The resin substrate (support) used in the present invention can be produced by a conventionally known general method. For example, an unstretched resin base material (support) that is substantially amorphous and not oriented is manufactured by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. Can do.

  Further, an unstretched resin base material (support) is obtained by a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. ) In the flow (vertical axis) direction or in the direction perpendicular to the flow direction of the resin substrate (support) (horizontal axis), a stretched support can be produced.

  The draw ratio in this case can be appropriately selected according to the resin used as the raw material of the resin base material (support), but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively.

  Furthermore, in order to improve the dimensional stability of the substrate in the stretched film, it is preferable to perform a relaxation treatment after stretching.

  Moreover, in the resin base material (support body) based on this invention, you may corona-treat before forming a coating film. Furthermore, an anchor coating agent layer may be formed on the surface of the support according to the present invention for the purpose of improving the adhesion to the coating film.

《Anchor coating agent layer》
Examples of the anchor coating agent used in the 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. One or two or more can be used 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).

《Smooth layer》
The gas barrier film of the present invention may have a smooth layer. The smooth layer used in the present invention flattens the rough surface of the transparent resin film support with protrusions or the like, or fills the irregularities and pinholes generated in the transparent inorganic compound layer with the protrusions present on the transparent resin film support. Provided for flattening. Such a smooth layer is basically produced 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 method for forming the smooth layer is not particularly limited, but it is preferably formed by a wet coating method such as a spray method, a blade coating method, or a dip method, or a dry coating method such as a vapor deposition 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 the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. If 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 in the coating method such as a wire bar or wireless bar at the stage of coating the silicon compound described later. There is. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

<Bleed-out prevention layer>
The bleed-out prevention layer used in the present invention suppresses a phenomenon in which, when a film having a smooth layer is heated, unreacted oligomers migrate from the film support to the surface and contaminate the contact surface. For this purpose, it is provided on the opposite surface of the resin substrate having a smooth layer. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule or one in the molecule. And monounsaturated organic compounds having a 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 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 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than mass parts, more preferably not more than 16 mass parts.

  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 in a wavelength region 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 film, facilitates the balance adjustment of the optical characteristics of the film, and prevents curling when the bleed-out prevention layer is provided only on one side of the gas barrier film. From the viewpoint, a range of 1 to 10 μm is preferable, and a range of 2 to 7 μm is more preferable.

<< Coating film containing inorganic precursor compound >>
The coating film containing the inorganic precursor compound according to the present invention is formed by applying a coating liquid containing at least one inorganic precursor compound on the resin substrate.

  Any appropriate method can be adopted as a coating method. Specific examples include a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness can be set so that the thickness after drying is preferably about 1 nm to 10 μm, more preferably about 10 nm to 10 μm, and most preferably about 30 nm to 1 μm.

  The inorganic precursor compound according to the present invention is not particularly limited as long as it is a compound capable of forming a metal oxide, a metal nitride, or a metal oxynitride by vacuum ultraviolet irradiation under a specific atmosphere, but the production method of the present invention As a compound suitable for the above, a compound which can be modified at a relatively low temperature as described in JP-A-8-112879 is preferable.

  Specifically, polysiloxane (including polysilsesquioxane) having Si—O—Si bond, polysilazane having Si—N—Si bond, both Si—O—Si bond and Si—N—Si bond Polysiloxazan containing can be raised. These can be used in combination of two or more. Moreover, it can be used even if different compounds are sequentially laminated or simultaneously laminated.

(Polysiloxane)
The polysiloxane used in the present invention can include [R ₃ SiO _1/2 ], [R ₂ SiO], [RSiO _3/2 ], and [SiO ₂ ] as general structural units. R is independently selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 20 carbon atoms such as methyl, ethyl, propyl, etc., an aryl group such as phenyl, and an unsaturated alkyl group such as vinyl. . Examples of specific polysiloxane groups include [PhSiO _3/2 ], [MeSiO _3/2 ], [HSiO _3/2 ], [MePhSiO], [Ph ₂ SiO], [PhViSiO], [ViSiO _3/2 ]. ], [MeHSiO], [MeViSiO], [Me ₂ SiO], [Me ₃ SiO _1/2 ] and the like. Mixtures and copolymers of polysiloxanes can also be used.

(Polysilsesquioxane)
In the present invention, it is preferable to use polysilsesquioxane among the above-mentioned polysiloxanes. Polysilsesquioxane is a compound containing silsesquioxane in a structural unit. “Silsesquioxane” is a compound represented by [RSiO _3/2 ], usually RSiX ₃ (R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an araalkyl group, etc. Is a polysiloxane synthesized by hydrolysis-polycondensation of a type compound (such as a halogen or an alkoxy group). The shape of the molecular arrangement of cissesoxane is typically an amorphous structure, a ladder structure, a cage structure or a partially cleaved structure thereof (a structure in which one silicon atom is missing from the cage structure or a part of the cage structure) A structure in which a silicon-oxygen bond is broken is known.

Among these polysilsesquioxanes, it is preferable to use a so-called hydrogen silsesquioxane polymer. Hydrogen silsesquioxane polymers include hydridosiloxane polymers of the formula: HSi (OH) _x (OR) _y O _{z / 2} where each R is an organic group or a substituted organic group, When bonded to silicon, it forms a hydrolyzable substituent, where x = 0-2, y = 0-2, z = 1-3, x + y + z = 3. Examples of R include alkyl groups such as methyl, ethyl, propyl, butyl and the like, aryl groups such as phenyl, alkenyl groups such as allyl and vinyl. As such, these resins may be fully condensed (HSiO _3/2 ) _n , or only partially hydrolyzed (ie, including some Si-OR) and / or partially condensed. (Ie, including some Si—OH).

Examples of the cage silsesquioxane include silsesquioxane of the following general formula (1) represented by the chemical formula of [RSiO _3/2 ] _{8 and} the following chemical formula of [RSiO _3/2 ] ₁₀ Silsesquioxane of general formula (2), represented by the chemical formula of [RSiO _3/2 ] ₁₂ Silsesquioxane of general formula (3), represented by the chemical formula of [RSiO _3/2 ] ₁₄ Silsesquioxane of general formula (4), silsesquioxane of the following general formula (5) represented by the chemical formula of [RSiO _3/2 ] ₁₆ may be mentioned.

The _{[RSiO 3/2]} value of n in the cage-type silsesquioxane represented by _n is an integer of 6 to 20, preferably 8, 10 or 12, particularly preferably 8 or 8,10 And 12 mixtures. In addition, [RSiO _3/2 ] _nm (O _1/2 H) _{2 + m} (n is an integer of 6 to 20) in which part of the silicon-oxygen bond of the cage silsesquioxane is partially cleaved. m is 0 or 1. As a preferable example of the cage silsesquioxane represented by the following formula, a trisilanol body in which a part of the general formula (1) is cleaved, [RSiO _3/2 ] ₇ (O _{1 /} 2H) Silsesquioxane of the following general formula (6) represented by _3; Silsesquioxane of the following general formula (7) represented by the chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) ₂ Oxane, silsesquioxane of the following general formula (8) represented by the chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) ₂ may be mentioned.

  R in the general formulas (1) to (8) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an araalkyl group having 7 to 20 carbon atoms, or 6 to 6 carbon atoms. There are 20 aryl groups. Among these, R is preferably a polymerizable functional group capable of polymerization reaction.

  Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group (n-butyl group, i-butyl group, t-butyl group, sec -Butyl group, etc.), pentyl group (n-pentyl group, i-pentyl group, neopentyl group, cyclopentyl group etc.), hexyl group (n-hexyl group, i-hexyl group, cyclohexyl group etc.), heptyl group (n- Heptyl group, i-heptyl group, etc.), octyl group (n-octyl group, i-octyl group, t-octyl group, etc.), nonyl group (n-nonyl group, i-nonyl group, etc.), decyl group (n- Decyl group, i-decyl group, etc.), undecyl group (n-undecyl group, i-undecyl group, etc.), dodecyl group (n-dodecyl group, i-dodecyl group, etc.) and the like. In consideration of the balance of melt fluidity, flame retardancy and operability during molding, it is preferably a saturated hydrocarbon having 1 to 16 carbon atoms, particularly preferably a saturated hydrocarbon having 1 to 12 carbon atoms.

  Examples of the alkenyl group having 2 to 20 carbon atoms include acyclic alkenyl groups and cyclic alkenyl groups. Examples thereof include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, A dodecenyl group etc. are mentioned. In consideration of the balance of melt fluidity, flame retardancy and operability during molding, an alkenyl group having 2 to 16 carbon atoms is preferable, and an alkenyl group having 2 to 12 carbon atoms is particularly preferable.

  Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, or a benzyl group, a phenethyl group, etc., which are substituted by 1 or more carbon atoms among alkyl groups having 1 to 13 carbon atoms, preferably 1 to 8 carbon atoms. Is mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, or a phenyl group substituted with an alkyl group having 1 to 14 carbon atoms, preferably 1 to 8 carbon atoms, a tolyl group, and a xylyl group. It is done.

  As the above-described cage-type silsesquioxanes, compounds commercially available from Aldrich, Hybrid Plastic, Chisso, Amax, etc. may be used as they are, and Journal of American Chemical Society, Vol. 111 1741 (1989), etc., may be used.

The partial cleavage structure having a cage structure of polysilsesquioxane is Si—O—Si bond generated by cleavage of a Si—O—Si bond from one cage unit represented by the chemical formula [RSiO _3/2 ] _8. A compound having 3 or less OH or a compound having 1 or less Si atom deficiency in a closed cage structure represented by the chemical formula [RSiO _3/2 ] ₈ is shown.

Also in the cage silsesquioxane, hydrogen silsesquioxane such as [HSiO _3/2 ] ₈ can be preferably used.

(Polysilazane)
The polysilazane used in the present invention is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N ₄ and both intermediate solid solutions SiO _x N _y (x : 0.1-1.9, y: 0.1-1.3).

  The polysilazane preferably used in the present invention is represented by the following general formula (A).

Formula (A)
-[Si (R ₁ ) (R ₂ ) -N (R ₃ )]-
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as the resulting barrier film.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base substrate is improved and the polysilazane is hard and brittle. Since toughness can be imparted to the ceramic film, there is an advantage that generation of cracks can be suppressed even when the film thickness is increased. These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.

  As another example of polysilazane which is ceramicized at low temperature, silicon alkoxide-added polysilazane obtained by reacting silicon alkoxide with the above polysilazane (Japanese Patent Laid-Open No. 5-23827), glycidol-added polysilazane obtained by reacting glycidol (special (Kaihei 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-299118). No. 1), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (Japanese Patent Laid-Open No. 19698 JP), and the like.

  As an organic solvent for preparing a liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers can be used. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of solvents may be mixed.

  The polysilazane concentration in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the target silica film thickness and the pot life of the coating solution.

  The organic polysilazane may be a derivative in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like. By having an alkyl group, especially a methyl group having the smallest molecular weight, the adhesion to the base material can be improved, and the hard and brittle silica film can be toughened, and even if the film thickness is increased, cracks are not generated. Occurrence is suppressed.

  An amine or metal catalyst may be added in order to accelerate the modification treatment to the silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd.

(Polysiloxazan)
In the polysiloxazan according to the present invention, main repeating units are — [(SiH ₂ ) _n (NH) _r ] — and — [(SiH ₂ ) _m O] — (wherein n, m and r are 1, 2 or It is a compound shown by 3).

(catalyst)
A catalyst can be added to the solution containing the inorganic precursor according to the present invention (also referred to as a coating solution) as necessary.

  Specifically, 1-methylpiperazine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 4,4′-trimethylenebis (1-methylpiperidine), diazabicyclo- [2,2,2] Octane, cis-2,6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, pyridine, dipyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4′- N-heterocyclic compounds such as trimethylenedipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, 1-methylpyrrolidine; methylamine, dimethylamine , Trimethylamine, ethylamine, diethylamino , Triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, octyl Amines such as amine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine; DBU (1,8-diazabicyclo [5,4,0] 7-undecene), DBN (1,5-diazabicyclo [ 4,3,0] 5-nonene), 1,5,9-triazacyclododecane, 1,4,7-triazacyclononane and the like.

Organic acids, inorganic acids, metal carboxylates, acetylacetona complexes, and metal fine particles are also preferable catalysts. Organic acids include acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, stearic acid, and inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, hypochlorous acid, etc. Is mentioned. The metal carboxylate is represented by the formula: (RCOO) _n M [wherein R represents an aliphatic group or an alicyclic group and represents one having 1 to 22 carbon atoms, and M represents Ni, Ti, Pt, Rh. Represents at least one metal selected from the group consisting of Co, Fe, Ru, Os, Pd, Ir, and Al, and n is the valence of M. It is a compound represented by. The metal carboxylate may be an anhydride or a hydrate. The acetylacetona complex is a complex in which an anion acac ⁻ generated by acid dissociation from acetylacetone (2,4-pentadione) is coordinated to a metal atom, and generally has the formula (CH ₃ COCHCOCH ₃ ) _n M [Wherein M represents a metal having an ionic value of n. Suitable metals M include, for example, nickel, platinum, palladium, aluminum, rhodium and the like. As the metal fine particles, Au, Ag, Pd, and Ni are preferable, and Ag is particularly preferable. The particle diameter of the metal fine particles is preferably smaller than 0.5 μm, more preferably 0.1 μm or less, and further preferably smaller than 0.05 μm. In addition to these, organic metal compounds such as peroxide, metal chloride, ferrocene, zirconocene, and the like can also be used. Further, platinum vinyl siloxane used as a curing agent for silicone polymer can also be used.

  These catalysts are preferably blended in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, based on the inorganic precursor compound.

(Overcoat layer)
In the gas barrier film of the present invention, an overcoat layer may be provided on the outermost gas barrier layer.

(Material used for overcoat layer)
As the organic material used for the overcoat layer, organic resins such as organic monomers, oligomers, and polymers can be preferably used. These organic resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins, and are formed by coating from an organic resin composition coating solution containing a polymerization initiator, a crosslinking agent, or the like as necessary. The layer is preferably cured by applying light irradiation treatment or heat treatment. Here, the “crosslinkable group” is a group that can crosslink the binder polymer by a chemical reaction that occurs during light irradiation treatment or heat treatment. The chemical structure is not particularly limited as long as it is a group having such a function. Examples of the functional group capable of addition polymerization include cyclic ether groups such as an ethylenically unsaturated group and an epoxy group / oxetanyl group. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen atom, an onium salt structure etc. are mentioned, for example. Among these, an ethylenically unsaturated group is preferable and includes functional groups described in paragraphs 0130 to 0139 of JP2007-17948A.

  The elastic modulus of the overcoat layer can be adjusted to a desired value by appropriately adjusting the structure of the organic resin, the density of the polymerizable group, the density of the crosslinkable group, the ratio of the crosslinking agent, and the curing conditions.

  Specific examples of the organic resin composition include 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, and urethane acrylate. And 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.

  Examples of the reactive monomer having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n- Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, di Cyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, group Sidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripro Lenglycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2 , 4 -Trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane , 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator. As photopolymerization initiators, benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert- Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin methyl Ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azidobenzylidene ) Cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- ( o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, mihi -Ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride, Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide, Examples include a combination of a photoreducible pigment such as eosin and methylene blue and a reducing agent such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more.

  The overcoat layer according to the present invention can contain an inorganic material. Inclusion of an inorganic material generally leads to an increase in the elastic modulus of the overcoat layer. The elastic modulus of the overcoat layer can also be adjusted to a desired value by appropriately adjusting the content ratio of the inorganic material.

  As the inorganic material, inorganic fine particles having a number average particle diameter of 1 to 200 nm are preferable, and inorganic fine particles having a number average particle diameter of 3 to 100 nm are more preferable. As the inorganic fine particles, metal oxides are preferable from the viewpoint of transparency.

_{There is} no particular restriction as the metal _{oxide, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, ZnO, SnO 2, In 2 O 3, BaO, SrO, CaO, MgO, VO 2, V 2 O 5, _{CrO 2, MoO 2, MoO 3} , MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO 4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O 5, Examples thereof include Cd ₂ SnO ₄ , CdIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , and Zn ₂ In ₂ O ₅ . These may be used alone or in combination of two or more.

  In order to obtain a dispersion of inorganic fine particles, it may be adjusted according to recent academic papers, but commercially available inorganic fine particle dispersions can also be preferably used.

  Specific examples include dispersions of various metal oxides such as Snowtex series and organosilica sol manufactured by Nissan Chemical Industries, NANOBYK series manufactured by Big Chemie Japan, and NanoDur manufactured by Nanophase Technologies.

  These inorganic fine particles can also be used after surface treatment.

As the inorganic material, mica groups such as natural mica and synthetic mica, and tabular fine particles such as talc, teniolite, montmorillonite, saponite, hectorite, zirconium phosphate represented by the formula 3MgO · 4SiO · H ₂ O may be used. it can.

Specifically, examples of the natural mica include muscovite, soda mica, phlogopite, biotite and sericite. Synthetic mica includes fluorine phlogopite KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg ₂ . Non-swelling mica such as 5Si ₄ O ₁₀ ) F ₂ , and Na tetrasilicic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) _{F 2,} montmorillonite of Na or Li hectorite _{(Na, Li) 1 / 8Mg} 2 / 5Li 1/8 (Si 4 O 10) swelling mica _{F 2.} Synthetic smectite is also useful.

  The ratio of the inorganic material in the overcoat layer is preferably in the range of 10 to 95% by mass, and more preferably in the range of 20 to 90% by mass with respect to the entire overcoat layer.

  The overcoat layer is blended with the organic resin and the inorganic material, and other components as necessary, and prepared as a coating solution by using a diluting solvent as necessary, and the coating solution is conventionally applied to the resin substrate surface. It is preferable to form by applying ionizing radiation after being applied by a known application method and then curing. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region 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. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

(Use of gas barrier film)
The gas barrier film of the present invention is mainly a package for electronic devices or the like, or a gas barrier film used for display materials such as plastic substrates for organic EL elements, solar cells, liquid crystals and the like, and a resin base for various devices using the gas barrier film. It can be applied to materials and various device elements.

  The gas barrier film of the present invention can be preferably applied as various sealing materials and films.

(Organic photoelectric conversion element)
The organic photoelectric conversion element can have the gas barrier film of the present invention as a constitution. When used in an organic photoelectric conversion element, the gas barrier film is transparent, so that the gas barrier film can be used as a resin base material to receive sunlight from this side.

  That is, on this gas barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin support for an organic photoelectric conversion element.

  Then, an ITO transparent conductive film provided on the support is used as an anode, a porous semiconductor layer is provided thereon, a cathode made of a metal film is further formed to form an organic photoelectric conversion element, and another seal is formed thereon. The organic photoelectric conversion element can be sealed by stacking a stop material (although it may be the same), adhering the gas barrier film support and the periphery, and encapsulating the element. The influence on the element due to can be sealed.

  The resin support for an organic photoelectric conversion element is a ceramic layer of a gas barrier film formed in this way (here, the ceramic layer includes a silicon oxide layer formed by modifying a polysilazane layer). It is obtained by forming a transparent conductive film on the top.

  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.

  Moreover, as a film thickness of a transparent conductive film, the transparent conductive film of the range of 0.1-1000 nm is preferable.

  Next, each layer (constituent layer) of the organic photoelectric conversion element material constituting the organic photoelectric conversion element will be described.

(Configuration of organic photoelectric conversion element and solar cell)
The preferable aspect of an organic photoelectric conversion element and a solar cell is demonstrated. In addition, although the preferable aspect of an organic photoelectric conversion element is demonstrated in detail hereafter, the said solar cell has the said organic photoelectric conversion element as the structure, and the preferable structure of a solar cell can also be described similarly.

  The organic photoelectric conversion element is not particularly limited, and includes at least one anode and a cathode, and a power generation layer (a layer in which a p-type semiconductor and an n-type semiconductor are mixed, a bulk heterojunction layer, or an i layer) sandwiched between the anode and the cathode. Any element that generates current when irradiated with light may be used.

  The preferable specific example of the layer structure of an organic photoelectric conversion element (The preferable layer structure of a solar cell is also the same) is shown below.

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

(I) Anode / power generation layer / cathode (ii) Anode / hole transport layer / power generation layer / cathode (iii) Anode / hole transport layer / power generation layer / electron transport layer / cathode (iv) Anode / hole transport layer / P-type semiconductor layer / power generation layer / n-type semiconductor layer / electron transport layer / cathode (v) anode / hole transport layer / first power generation layer / electron transport layer / intermediate electrode / hole transport layer / second power generation layer / Electron transport layer / cathode.

  Here, the power generation layer needs to contain a p-type semiconductor material capable of transporting holes and an n-type semiconductor material capable of transporting electrons. Alternatively, a bulk heterojunction that is in a mixed state in one layer may be manufactured, but a bulk heterojunction configuration is preferable because of higher photoelectric conversion efficiency. A p-type semiconductor material and an n-type semiconductor material used for the power generation layer will be described later.

  Like the organic EL element, the efficiency of taking out holes and electrons to the anode / cathode can be increased by sandwiching the power generation layer between the hole transport layer and the electron transport layer. Therefore, the structure having them ((ii), ( iii)) is preferred. 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). Configuration (also referred to as “p-i-n 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.

  Below, the material which comprises these layers is described.

(Organic photoelectric conversion element material)
A material used for forming the power generation layer (also referred to as “photoelectric conversion layer”) of the organic photoelectric conversion element will be described.

(P-type semiconductor material)
Examples of the p-type semiconductor material preferably used as the power generation layer (bulk heterojunction layer) of the organic photoelectric conversion element 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 described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; 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.

  Examples of the conjugated polymer include 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, p328, a polythiophene-thienothiophene copolymer, a polythiophene-diketopyrrolopyrrole copolymer described in WO08 / 000664, and 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 is possible and that can produce a crystalline thin film and achieve high mobility after drying 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 a material include materials that can be insolubilized by polymerizing and crosslinking 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 Japanese Patent Application Laid-Open No. 2008-16834, etc., the soluble substituent reacts to insolubilize ( And materials).

(N-type semiconductor material)
Although it does not specifically limit as n-type semiconductor material used for a bulk heterojunction layer, For example, perfluoro body (Perfluoropentacene, perfluorophthalocyanine, etc.) which substituted the hydrogen atom of the p-type semiconductor with the fluorine atom, such as fullerene and octaazaporphyrin ), Aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and polymer compounds containing the imidized product as a skeleton. be able to.

  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), and the like. Some are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cycloalkyl groups, silyl groups, ether groups, thioether groups, amino groups, silyl groups, etc. Examples thereof include substituted fullerene derivatives.

Among them, [6,6] - phenyl _{C 61} - butyric acid methyl ester (abbreviation PCBM), [6,6] - phenyl _{C 61} - butyric acid -n-butyl ester (PCBnB), [6,6] - phenyl C ₆₁ - butyric acid - isobutyl ester (PCBiB), [6,6] - phenyl _{C 61} - 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)
The organic photoelectric conversion element has a hole transport layer between the bulk heterojunction layer and the anode, and it is possible to extract charges generated in the bulk heterojunction layer more efficiently. It is preferable.

  Examples of the material constituting these layers include, as the hole transport layer, PEDOT such as StarkVutec, trade name BaytronP, polyaniline and its doped material, cyan described in WO06 / 19270, etc. Compounds, etc. 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. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable. It is preferable to produce a coating film in the lower layer before producing the bulk heterojunction layer because it has the effect of leveling the application surface and reduces the influence of leakage and the like.

(Electron transport layer / hole blocking layer)
An organic photoelectric conversion device has an electron transport layer in the middle of the bulk heterojunction layer and the cathode, so that charges generated in the bulk heterojunction layer can be taken out more efficiently. It is preferable.

  As the electron transport layer, octaazaporphyrin and p-type semiconductor perfluoro (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, HOMO of p-type semiconductor material used for the bulk heterojunction layer. The electron transport layer having a HOMO level deeper than the 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. As a means for producing these layers, either a vacuum vapor deposition method or a solution coating method may be used, but a solution coating method is preferable.

(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))
The transparent electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration. Preferably, the transparent electrode is used as an 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 producing a thin film of 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.

  The counter electrode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticle, nanowire, or nanostructure. If the dispersion is, a transparent and highly conductive counter electrode can be produced 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)
Moreover, as a material of the intermediate electrode required in the case of the tandem configuration as in (v) of the layer configuration of the organic photoelectric conversion element, a layer using a compound having both transparency and conductivity is preferable. Materials used in the transparent electrode (transparent metal oxides such as ITO, AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, PEDOT: PSS, conductive polymer materials such as polyaniline, etc.) 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 stacking in an appropriate combination. This is preferable because it can be omitted.

(Metal nanowires)
As the conductive fibers, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used, but metal nanowires are preferable.

  In general, the 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.

  As a metal nanowire, in order to produce a long conductive path with one metal nanowire and to express appropriate light scattering properties, the average length is preferably 3 μm or more, and more preferably 3 μm to 3 μm 500 μm is preferable, and 3 μm to 300 μm is particularly preferable. 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 the present invention, the average diameter of the metal nanowire is preferably 10 nm to 300 nm, and more preferably 30 nm to 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 metal nanowire, Although it can comprise from the 1 type or several metal of a noble metal element or a base metal element, it is noble metal (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, and more preferably at least silver 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. You may have.

  There is no restriction | limiting in particular in the manufacturing method of metal nanowire, For example, well-known means, such as a liquid phase method and a gaseous-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 manufacturing method of Ag nanowire, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc., as a method for producing Au nanowires, such as JP 2006-233252A, etc., as a method for producing Cu nanowires, JP 2002-266007 A, etc. For example, Japanese Patent Application Laid-Open No. 2004-149871 can be referred to. 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 production of metal nanowires according to the present invention is possible. It can be preferably applied as a method.

  Metal nanowires come into contact with each other to create a three-dimensional conductive network, exhibiting high conductivity, and allowing light to pass through the conductive network window where no metal nanowire exists, Due to the scattering effect of the metal nanowires, it is possible to efficiently generate power from the organic power generation layer. 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 may have various optical functional 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 is smaller than this, the effect of diffraction is generated and colored, and if it is too large, the thickness becomes thick, which 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 producing 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 producing 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 inkjet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, a flexographic printing method, or the like.

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

(Patterning)
There is no particular limitation on the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like, and known methods can be applied as appropriate.

  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, mask evaporation can be performed during vacuum deposition of the electrode, or patterning can be performed by a known method such as etching or lift-off. Alternatively, the pattern may be produced by transferring a pattern produced on another substrate.

  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 1 >>
As described below, first, a resin base material is prepared, and then a layer containing an inorganic precursor compound is applied and formed on the resin base material. A conductive film was prepared.

<< Production of Resin Base Material 1 >>
Using a polyester film with a width of 500 mm and a thickness of 125 μm that is easily bonded on both sides (Teijin DuPont Films Co., Ltd., extremely low heat yield PET Q83), as shown below, a bleed-out prevention layer on one side and an opposite side A smooth layer was produced to obtain a resin substrate 1.

(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Co., Ltd. is applied to one side of the resin base material, and the film thickness after drying is 4 μm, followed by curing conditions: 1.0 J / cm ^2. Using a high-pressure mercury lamp in an air atmosphere, drying conditions: Curing was performed at 80 ° C. for 3 minutes to form a bleedout prevention layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Co., Ltd. was applied to the opposite surface of the resin substrate, and the film thickness after drying was 4 μm, followed by drying conditions: 80 ° C. After drying in 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions; 1.0 J / cm ² to form a smooth layer.

  The obtained smooth layer had a surface roughness specified by JIS B 0601 and a maximum cross-sectional height Rt (p) of 16 nm.

  The surface roughness was measured using an AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII. The measurement range at one time was 80 μm × 80 μm, and the measurement location was changed three times, and the average of the Rt values obtained in each measurement was taken as the measurement value.

  The thickness of the resin base material 1 is 133 μm.

<< Production of Resin Base Material 2 >>
A resin substrate 2 was obtained in the same manner as the resin substrate 1 except that the polyester film having a thickness of 125 μm of the resin substrate 1 was changed to a 50 μm polyester film. The Rt of the resin substrate 2 was 16 nm, the same as that of the resin substrate 1.

  The thickness of the resin base material 2 is 58 μm.

<< Production of gas barrier layer >>
(Coating and drying process and modification process by vacuum ultraviolet irradiation)
As described below, gas barrier films of Samples 1 to 12 shown in Table 1 in which two 150 nm gas barrier layers were laminated were prepared.

  The modification treatment process by vacuum ultraviolet irradiation was performed by the vacuum ultraviolet irradiation apparatus shown in the schematic diagram of FIG.

<Preparation of the first gas barrier layer>
<Application>
A vacuum extrusion type coater (not shown) containing a coating solution containing an inorganic precursor compound, which will be described later, on the smooth layer surface of the resin base material produced as described above, which is continuously conveyed from an unillustrated unwinding core at a speed of 1 m / min. The first gas barrier layer was applied so that the dry film thickness was 150 nm.

<Dry>
After coating, this was also dried by a drying apparatus not shown. As drying conditions, the drying time was 300 seconds, the drying temperature was adjusted to 80 ° C., and the dew point of the drying atmosphere was adjusted to 5 ° C.

<Modification treatment: 1st time>
After drying, the resin base material was gradually cooled to 25 ° C., and then a modification treatment was performed on the coated surface by irradiation with vacuum ultraviolet rays in a vacuum ultraviolet irradiation apparatus.

  Here, in each of the coating, drying, and modification processes, the same tension is applied by a tension control mechanism (not shown).

  In FIG. 1, 1 is a substrate, 2 is a Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and 3 is an excimer lamp holder that also serves as an external electrode.

  The Xe excimer lamp having a double tube structure can adjust the lamp tube surface temperature by flowing the pure water whose temperature is adjusted inside the double tube at a controlled flow rate by a temperature control mechanism (not shown). It is. The lamp temperature control mechanism will be described later.

  The lamp tube surface temperature is adjusted over 10 minutes after the lamp is turned on, and control parameters (temperature and flow rate of pure water) at each set temperature are collected in advance. The shortest distance between the lamp tube surface and the resin base material application surface was set in each condition so as to be the same value for all the lamps.

  In a combination of the conditions of the lamp tube surface temperature, the shortest distance between the pump tube surface and the resin base material application surface, the integrated energy of vacuum ultraviolet irradiation during 1 m / min conveyance was measured in advance. The measurement was performed using a 172 nm sensor head using a UV integrating photometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the distance between the lamp tube surface and the measurement surface of the sensor head is set to a predetermined value, and the atmosphere between the lamp tube surface and the measurement surface of the sensor head is the same as the vacuum ultraviolet irradiation process. Nitrogen was supplied so as to obtain an oxygen concentration, and measurement was performed by moving the sensor head at a speed of 1 m / min.

  Reference numeral 4 denotes a chamber for maintaining a nitrogen atmosphere. By supplying nitrogen from a dry nitrogen supply port (not shown), the oxygen concentration in the chamber can be reduced. In this example, the oxygen concentration in the chamber was adjusted to 300 ppm or less.

  Reference numeral 5 denotes a transport roll. In FIG. 1, the arrow (→) represents the direction of conveyance of the resin base material, and in this figure, the free span conveyance from the top to the bottom is shown in the vertical direction. Also good.

  Here, FIG. 2 is a diagram schematically showing a cross-sectional structure in the lateral direction of the excimer lamp.

  Reference numeral 2 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm. Reference numeral 3 denotes an excimer lamp holder that also serves as an external electrode. 6 is an internal electrode. 7 is filled with Xe rare gas. 8 is supplied with pure water for temperature adjustment.

  FIG. 3 is a diagram schematically showing a cross-sectional structure in the lateral direction of the excimer lamp.

  Reference numeral 2 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm. Reference numeral 3 denotes an excimer lamp holder that also serves as an external electrode. 6 is an internal electrode. 7 is filled with Xe rare gas. 8 is supplied with pure water for temperature adjustment. Reference numeral 9 is a pipe for circulating pure water, and 10 is a connector between the pipe and a lamp. A pure water supply / circulation mechanism (not shown) conformed to the method described in Japanese Patent Application Laid-Open No. 2003-167100.

<Winding>
After the modification treatment, the substrate on which the gas barrier layer was formed was wound around a winding core (not shown). Here, it was considered that the sample 13 having a low conveyance tension was in contact with the lamp tube surface during conveyance, and the barrier layer surface was scratched.

<Modification treatment: Second time>
The wound core is transferred to the unwinding side, transported again by applying a speed of 1 m / min and a specific tension, applied, and passed through the drying process (same conditions as described above) for the second modification. A quality treatment step (predetermined conditions) was performed. Sample 13, which has a low conveyance tension, was considered to have contacted the lamp tube surface during conveyance, as in the first modification treatment, and the scratches on the barrier layer surface increased.

<Preparation of the second gas barrier layer>
Similarly, a second gas barrier layer was formed on the first gas barrier layer. Each condition was the same as the first layer.

  Gas barrier films of Samples 1 to 13 were obtained with combinations of resin base materials and various setting conditions as shown in Table 1. In Sample 13, which was a condition in which the transport tension was low when the first layer was produced, the coating property of the second layer was deteriorated due to the effect of scratches on the surface of the first barrier layer, resulting in coating unevenness.

(Preparation of coating solution 1 containing an inorganic precursor compound)
The coating liquid 1 containing an inorganic precursor compound contains a catalyst-free perhydropolysilazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NN120-20) and an amine catalyst in an amount of 5% by mass. By mixing a perhydropolysilazane 20% by mass dibutyl ether solution (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) and adjusting the amine catalyst to 1% by mass, further diluting with dibutyl ether It was prepared as a 5 mass% dibutyl ether solution.

(Water vapor barrier property evaluation sample preparation device)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was vapor-deposited in a size of 12 mm × 12 mm through the mask on the surface of the gas barrier film samples 1 to 13 produced.

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing. Four samples of water vapor barrier property evaluation samples were prepared at arbitrarily selected positions of each gas barrier film.

  The obtained sample was stored under high temperature and high humidity of 60 ° C. and 90% RH, and in each of 20 hours storage, 40 hours storage, and 60 hours storage, metal calcium corroded on the metal calcium deposition area of 12 mm × 12 mm. The area was calculated in%, and the average value of the four samples and the value of the sample with the most corroded area among the four samples were evaluated based on the following indices. The results are shown in Table 1.

(Evaluation index)
○: The area where metallic calcium corroded is less than 1%.

  (Triangle | delta): The area which metal calcium corroded is 1% or more and less than 5%.

  X: The area which metal calcium corroded is 5% or more.

Example 2
<< Production of gas barrier film 2 >>
In the same manner as in Example 1, except that the coating gas 2 containing the following inorganic precursor compound was used for the second gas barrier layer, and the conditions described in Table 1 were used as the modification treatment conditions, the gas barrier film 14 was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
(Preparation of coating solution 2 containing an inorganic precursor compound)
The coating liquid 2 containing an inorganic precursor compound contains an uncatalyzed perhydropolysilazane 20% by mass dibutyl ether solution (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst at 5% by mass. Perhydropolysilazane 20% by weight dibutyl ether solution (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed and used to adjust the amine catalyst to 1% by weight of solid content. Sun (20% by mass MIBK solution) was added so as to have a solid content ratio of 50% by mass, and further diluted with dibutyl ether to prepare a 5% by mass dibutyl ether / MIBK mixed solution.

Example 3
<< Production of gas barrier film 3 >>
In the same manner as in Example 1, except that the coating gas 3 containing the following inorganic precursor compound was used for the second gas barrier layer and the conditions described in Table 1 were used as the modification treatment conditions, the gas barrier film 15 was obtained. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
(Preparation of coating solution 3 containing an inorganic precursor compound)
The coating liquid 3 containing an inorganic precursor compound contains a non-catalytic perhydropolysilazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd. Aquamica NN120-20) and an amine catalyst in an amount of 5% by mass. This is a hydrogen silsesquioxane polymer after adjusting the amine catalyst to 1% by mass of solid content by mixing 20% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.). Add Fox-14 (Toray Dow Corning, 14% by weight MIBK solution) to a solid content ratio of 50% by weight, and dilute with dibutyl ether to prepare a 5% by weight dibutyl ether / MIBK mixed solution. did.

  As shown in Table 1, it can be seen that the gas barrier film of the present invention achieves both high barrier properties and sufficient production stability.

Example 4
<Evaluation as a gas barrier film for organic thin film devices>
Using the produced gas barrier film as a sealing film, an organic photoelectric conversion element and an organic light emitting element are produced, and these are subjected to an accelerated deterioration treatment in a 60 ° C. and 90% RH environment for 200 hours, and compared with the performance before the accelerated deterioration. The gas barrier performance and its stability were evaluated.

<Evaluation of organic thin film element>
In the evaluation, each element was ranked according to the following criteria. The practical range is more than ○.

(Evaluation of organic photoelectric conversion element)
A solar simulator (AM1.5G filter) is irradiated with light of 100 mW / cm ² , a mask with an effective area of 4.0 mm ² is superimposed on the light receiving part, and IV characteristics are evaluated, whereby the short circuit current density Jsc ( mA / cm ² ), open-circuit voltage Voc (V), and fill factor FF (%) were measured for each of four light receiving portions formed on the same element, and energy conversion efficiency PCE (%) determined according to the following formula A The four-point average value was estimated.

(Formula A)
PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency maintenance ratio of the element after acceleration deterioration was calculated with respect to the element before acceleration deterioration, and was ranked as follows. The results are shown in Table 2.

Conversion efficiency maintenance ratio = element conversion efficiency after acceleration degradation processing / element conversion efficiency before acceleration degradation processing × 100 (%)
◎: 90% or more ○: 60% or more, less than 90% △: 20% or more, less than 60% ×: less than 20% (Evaluation of organic EL element)
(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the sample to emit light continuously for 24 hours, and then a part of the panel was magnified with a 100 × microscope (Mortex Co., Ltd. MS-804, lens MP-ZE25-200) and photographed. Went. The photographed image was cut out in a 2 mm square, visually observed, the situation of black spots was examined, the deterioration rate of the elements was calculated, and the following ranking was performed. The results are shown in Table 2.

Deterioration rate = area of black spots generated in the element before accelerated deterioration processing / area of black spots generated in the element after accelerated deterioration processing × 100 (%)
◎: 90% or more ○: 60% or more, less than 90% Δ: 20% or more, less than 60% ×: less than 20% <Method for producing organic photoelectric conversion element>
A gas barrier film having an indium tin oxide (ITO) transparent conductive film deposited to a thickness of 150 nm (sheet resistance 10 Ω / □) is patterned to a width of 2 mm using a normal photolithography technique and wet etching. An electrode was produced.

  The patterned first electrode was washed 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 subjected to ultraviolet ozone cleaning.

  On this transparent substrate, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, was applied and dried to a film thickness of 30 nm, and then heat treated at 150 ° C. for 30 minutes to form a hole transport layer. .

  Thereafter, the substrate was brought into a nitrogen chamber and manufactured 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 3.0% by mass of chlorobenzene. A liquid mixed at 1: 0.8 was prepared so that the film thickness was 100 nm while being filtered through a filter, and the film was allowed to stand at 25 ° C. and dried. Subsequently, a heat treatment was performed at 150 ° C. for 15 minutes to form a photoelectric conversion layer.

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

  Each of the obtained organic photoelectric conversion elements was moved to a nitrogen chamber and sealed according to the following procedure to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Preparation of gas barrier film sample for sealing and sealing of organic photoelectric conversion element)
In an environment purged with nitrogen gas (inert gas), two gas barrier films were used, and a surface on which a gas barrier layer was provided and an epoxy photocurable adhesive applied as a sealant was sealed It was produced as a film for use.

  Next, the organic photoelectric conversion element is sandwiched and adhered between the adhesive-coated surfaces of the two gas barrier film samples coated with the adhesive, and then cured by irradiating UV light from one side of the substrate. The organic photoelectric conversion element was sealed.

<Method for producing organic EL element>
On the inorganic layer of the gas barrier film, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography to form a first electrode layer. The pattern was such that the light emission area was 50 mm square.

<Formation of hole transport layer>
On the 1st electrode layer of the barrier film in which the 1st electrode layer was formed, after apply | coating the coating liquid for hole transport layer formation shown below with an extrusion coater, it dried and formed the hole transport layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before coating the hole transport layer forming coating solution, cleaning surface modification treatment of the barrier film was carried out using a low pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

(Application conditions)
The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50%.

(Preparation of coating solution for hole transport layer formation)
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

(Drying and heat treatment conditions)
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

<Formation of light emitting layer>
Subsequently, on the hole transport layer of the barrier film 1 formed up to the hole transport layer, the following white light emitting layer forming coating solution was applied by an extrusion coater and then dried to form a light emitting layer. The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

(Coating liquid for white light emitting layer formation)
The host material HA is 1.0 g, the dopant material DA is 100 mg, the dopant material DB is 0.2 mg, the dopant material DC is 0.2 mg, and dissolved in 100 g of toluene to form a white light emitting layer. It was prepared as a coating solution.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

(Drying and heat treatment conditions)
After applying the white light emitting layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., followed by a temperature of 130 ° C. A heat treatment was performed to form a light emitting layer.

<Formation of electron transport layer>
Subsequently, after forming the light emitting layer, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

(Application conditions)
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

(Coating liquid for electron transport layer formation)
The electron transport layer was prepared by dissolving EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

(Drying and heat treatment conditions)
After applying the coating solution for forming the electron transport layer, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Subsequently, an electron injection layer was formed on the formed electron transport layer. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Subsequently, the second electrode forming material is formed on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa except for the portion that becomes the take-out electrode on the first electrode on the formed electron injection layer. A mask pattern was formed by vapor deposition so that a light emitting area was 50 mm square by using aluminum as an extraction electrode, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The barrier film 1 formed up to the second electrode was moved again to a nitrogen atmosphere and cut into a prescribed size to produce an organic EL device.

(Cutting method)
The cutting method is not particularly limited, but is preferably performed by ablation processing using a high energy laser such as an ultraviolet laser (for example, wavelength 266 nm), an infrared laser, a carbon dioxide gas laser or the like. Since the gas barrier film has an inorganic thin film that is easily broken, cracks may occur in detail when cut with a normal cutter. The same applies to not only cutting of the element but also cutting of the gas barrier film alone. Furthermore, the cracking at the time of cutting can also be suppressed by installing a protective layer containing an organic component on the surface of the inorganic layer.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm, Surface treatment NiAu plating) was connected.

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
A sealing member was bonded to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus, and the organic EL element 101 was manufactured.

  In addition, as a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), a polyethylene terephthalate (PET) film (12 μm thick) with an adhesive for dry lamination (two-component reaction type urethane adhesive). The laminate used (adhesive layer thickness 1.5 μm) was used.

  A thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil using a dispenser.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct-based curing accelerator After that, the sealing substrate is closely attached and arranged so as to cover the joint portion of the take-out electrode and the electrode lead, and pressure bonding conditions using the pressure roll, pressure roll temperature 120 ° C., pressure 0. Close sealing was performed at 5 MPa and an apparatus speed of 0.3 m / min.

  As is apparent from the table, it can be seen that the organic thin film device using the gas barrier film of the present invention has excellent performance.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Xe excimer lamp 3 Holder 4 Chamber 5 Transport roll 6 Internal electrode 7 Noble gas 8 Pure water 9 Piping 10 Connector

Claims (4)

A coating film is prepared by applying a solution containing an inorganic precursor compound onto a resin substrate conveyed while applying tension, and the coating film is modified by irradiating it with vacuum ultraviolet rays using an excimer lamp. In the method for producing a gas barrier film having at least one gas barrier layer formed by quality treatment,
The surface temperature of the excimer lamp is 150 ° C. or less, and the shortest distance between the excimer lamp surface and the resin substrate is 10 mm or less,
A gas barrier film satisfying the following equation [1], where A (μm) is the thickness of the resin substrate, and B (N) is the tension per m width when the vacuum ultraviolet ray is irradiated. Manufacturing method.
0.3 ≦ B / A ≦ 4.0... [1]   The method for producing a gas barrier film according to claim 1, wherein in the step of modifying, the resin base material is conveyed in a free span.   The method for producing a gas barrier film according to claim 1, wherein perhydropolysilazane is used as the inorganic precursor compound.   A gas barrier film produced by the method for producing a gas barrier film according to claim 1.

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