JP2011031610A - Barrier film, method for producing barrier film, and element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film which can achieve an extremely high barrier performance and a method for producing the barrier film, and further provide an element using the barrier film as a substrate. <P>SOLUTION: In the barrier film, the method for producing the barrier film and an organic photoelectric transducer, the barrier film with a barrier layer containing at least one layer of a Si atom and an oxygen atom on the substrate has an average density (g/cm<SP>3</SP>), located from the surface of the barrier layer to 20 nm, of 2.10 or more and 2.30 or less, and a ten points averaged roughness on the surface of the barrier layer, Rzjis, of 90 nm or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a barrier film used for a package such as an electronic device, or a material such as a plastic substrate such as an organic EL element, a solar cell, or a liquid crystal, a manufacturing method thereof, and an organic photoelectric conversion element, and further, various types using the barrier film. The present invention relates to a resin substrate for devices and various device elements.

  Conventionally, a barrier film in which a metal oxide thin film such as aluminum oxide, magnesium oxide, silicon oxide or the like is formed on the surface of a plastic substrate or film is used for packaging of articles and foods that require blocking of various gases such as water vapor and oxygen. It is widely used in packaging applications to prevent the alteration of industrial products and pharmaceuticals. In addition to packaging applications, it is used in liquid crystal display elements, solar cells, organic electroluminescence (EL) substrates, and the like.

  Aluminum foil is widely used as a packaging material in such fields, but disposal after use has become a problem, and it is basically opaque and the contents can be confirmed from the outside. In addition, the display material is required to be transparent and cannot be applied at all.

  In particular, transparent substrates that are being applied to display elements such as organic electroluminescence and liquid crystal, solar cells, etc., can be produced in roll-to-roll in addition to the demands for weight reduction and enlargement in recent years. In addition to high demands such as long-term reliability and high degree of freedom in shape, and the ability to display curved surfaces, film base materials such as transparent plastics are used instead of glass substrates that are heavy and easily broken Has begun to be adopted. For example, an example using a polymer film as a substrate is disclosed (for example, see Patent Documents 1 and 2). When the transparent resin film has a relatively high oxygen permeability such as polyethylene terephthalate (hereinafter abbreviated as “PET”), the film substrate such as a transparent plastic is inferior in gas barrier properties to glass. There's a problem. For example, when used as a substrate of an organic photoelectric conversion element, there is a problem that if a base material with poor gas barrier properties is used, water vapor or air penetrates and the performance is likely to deteriorate with time.

  In order to solve such problems, it is known to form a metal oxide thin film on a film substrate to form a barrier film substrate. Known barrier films used for packaging materials and liquid crystal display elements include those obtained by depositing silicon oxide on a plastic film (for example, see Patent Document 1) and those obtained by depositing aluminum oxide (for example, see Patent Document 2). ing.

  As an alternative to the vapor deposition method, there is a method in which a gas barrier layer is formed by a heat treatment after applying a coating liquid containing polysilazane as a main component. Polysilazane is known to be converted to silica at 400 to 500 ° C., but unlike glass substrates and silicon wafers, it can be applied from the viewpoint of heat resistance in film base materials such as transparent plastics that can be produced from roll to roll. There wasn't. In order to improve this point, various types of catalysts for lowering the conversion temperature have been studied. However, the catalyst remaining in the coating film has a problem that gas barrier properties and transparency are lowered. On the other hand, even when low-temperature treatment is possible, a new problem in production aptitude has been generated in which the treatment (conversion) time is increased accordingly.

Furthermore, the following techniques are known as surface treatments instead of heat treatments (see, for example, Patent Documents 3 and 4). These have the advantage of lowering the processing temperature for silica conversion, however, none of the techniques can increase the average density (g / cm ³ ) of the barrier layer to 2.10 or higher. The function of was insufficient. This is due to incomplete conversion to silica, residual impurities in the barrier layer, generation of voids due to volatilization of volatile substances, material composition that is insufficiently flexible, and inappropriate production methods (heat load is For example, a crack (crack) of the barrier layer caused by a large size).

Accordingly, there has been a demand for further improvement in gas barrier properties such that the water vapor transmission rate is significantly lower than 1 × 10 ⁻² g / m ² · day.

  As a technique for further improving the gas barrier property, a technique using the above-mentioned polysilazane layer in combination with a plasma chemical vapor deposition method is also known (for example, see Patent Document 5). However, even in this technique, the above-mentioned gas barrier property target has not been achieved.

  As a technique using a barrier film as an element, the following technique is known (for example, see Patent Document 6). In this case, sufficient crack resistance was not obtained when the barrier film was bent.

  The following techniques are known as a method for forming a functional body having a fine structure using a plasma chemical vapor deposition method with a silazane compound as a raw material and having peelability, scratch resistance, luminance life, transmittance, and light shielding properties (for example, Patent Document 7). The device fabricated using this technology has a good lifetime, but it is a problem unique to plasma chemical vapor deposition, a submicron to micron-size source reaction called particles in the plasma space between opposing electrodes. When product particles are generated and the particles adhere to the deposited film surface, the formation of a uniform film may be hindered, and there is a concern that the portion becomes a defect and the quality of the device is deteriorated.

  Further, since the particles are submicron (100 to 900 nm) to micron size, the surface roughness of the barrier layer, Rzjis is not less than submicron (100 to 900 nm), and the surface smoothness of the barrier film is improved. Due to the loss of formality, the barrier layer is easily cracked due to stress concentration with respect to bending, and improvement has been demanded.

JP-A-2-251429 JP-A-6-124785 JP 2007-237588 A JP 2000-246830 A Japanese Patent Laid-Open No. 8-281186 JP 2002-222691 A JP 2004-84027 A

  An object of the present invention is to provide a barrier film capable of achieving extremely high barrier performance and a method for producing the same, and further, an organic photoelectric conversion (OPV) device using the barrier film as a base material, and an organic electro The object is to provide a luminescence (EL) element.

  The above object of the present invention can be achieved by the following configuration.

1. A barrier film having a barrier layer containing at least one Si atom and oxygen atom on a substrate, wherein an average density from the surface of the barrier layer to 20 nm is 2.10 g / cm ³ or more and 2.30 g / cm ³ or less, and a barrier film ten-point average roughness of the surface layer of the barrier layer, the Rzjis is equal to or less than 90 nm.

  2. 2. The barrier film as described in 1 above, wherein the ten-point average roughness of the surface layer of the barrier layer, Rzjis, is 30 nm or less.

  3. 3. The barrier film as described in 1 or 2 above, wherein 1 to 6 barrier layers are further laminated on the barrier layer.

  4). 4. The barrier film according to any one of 1 to 3, wherein the substrate is polyethylene terephthalate (PET).

  5. The barrier film according to any one of 1 to 4 above, wherein the barrier film has a visible light transmittance of from 70% to 90% at 400 to 800 nm.

  6). The organic photoelectric conversion element or organic electroluminescent element characterized by using the barrier film of any one of said 1-5.

  7. The barrier film according to any one of 1 to 5 above, wherein a coating layer containing a silicon compound is applied on a base material and then subjected to a two-frequency plasma treatment in a discharge gas atmosphere to contain a silicon oxide. A method for producing a barrier film, which is produced by forming a film.

  8). 6. The barrier film according to any one of 1 to 5 above, after applying a coating solution containing a silicon compound on a substrate, a vacuum ultraviolet ray irradiation treatment is performed to form a barrier layer containing a silicon oxide. The manufacturing method of the barrier film characterized by the above-mentioned.

  According to the present invention, it is possible to obtain a barrier film that is excellent in production stability and handleability and can achieve high barrier performance, and is a barrier film useful as a resin substrate for an element excellent in high barrier properties, and a production method thereof, An organic photoelectric conversion element and an organic electroluminescence element can be obtained using the substrate.

It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is a figure which shows the structure of an optical sensor array.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  Conventionally, there has been a demand for a barrier substrate having a high water vapor barrier property applicable to various device elements and the like, which can use a transparent, plastic film that is lightweight, inexpensive, transparent, and roll-to-roll can be used as a substrate. Under such circumstances, polysilazane and the like can be converted to silica at 400 to 500 ° C. or higher to exhibit good barrier properties, but cannot be applied to general-purpose films (representative example PET) from the viewpoint of heat resistance. In order to improve this point, various catalysts for lowering the conversion temperature have been studied. However, the catalyst remaining / volatilized in the coating film has a problem that the barrier property and transparency are lowered. On the other hand, even when low-temperature treatment is possible, a new problem in production aptitude has been generated in which the treatment (conversion) time is increased accordingly.

  Further, as a surface treatment instead of the heat treatment, a single-frequency plasma treatment is known, and although there is an advantage of lowering the treatment temperature, the obtained barrier property is insufficient.

The present inventor determined that the average density of the surface layer of the barrier layer was 2.1 to 2.3 g by “Si, O-containing compound coating + double frequency plasma treatment” or “Si, O-containing compound coating + vacuum ultraviolet irradiation treatment”. The film can be converted to a dense film at a low temperature of / cm ³ and, in addition, has a high visible light transmittance (transparency) and is suitable for production (less heat and time load in production), and is further coated with a barrier layer in advance. By providing a film to be converted into a barrier layer, it becomes a barrier layer with high surface smoothness and high uniformity of film thickness, and since stress concentration is eased, it has excellent bending resistance and has good barrier properties even after bending. The barrier film of the invention could be made. Therefore, the organic photoelectric conversion element produced using the barrier film of the present invention and the organic electroluminescence element can provide an extremely excellent barrier film capable of roll-to-roll production.

  The barrier film of the present invention will be described. The barrier film of the present invention has a single ceramic layer on a resin film substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). Moreover, the barrier film of this invention may laminate | stack two or more ceramic layers, and the barrier film has a resin film base material and at least 1 layer of ceramic layers.

About the density (g / cm ³ ) of the barrier layer The barrier layer in the present invention is a film containing silicon atoms and oxygen atoms and blocking permeation of oxygen and water vapor, containing Si and O, and having a surface layer of the barrier layer. The average density (g / cm ³ ) of at least 20 nm is 2.10 or more and 2.30 or less.

As a more preferable range, the average density (g / cm ³ ) of at least 20 nm of the surface layer of the barrier layer is 2.15 or more and 2.25 or less.

  For example, if it is smaller than this range, if it is small, the conversion to the barrier layer is not completed, the low molecular weight catalyst remains in the barrier layer, the void is generated due to volatilization of the volatile catalyst, and the flexibility is insufficient. Examples include cracks in the barrier layer caused by the material composition and inappropriate production methods (such as a large heat load).

  On the other hand, in the case where it is large, the high molecular weight catalyst (containing metal, etc.) remains in the barrier layer.

Specifically, the constituent material is preferably an inorganic oxide having silicon, and examples thereof include ceramic layers such as silicon oxide and silicon oxynitride. With such a barrier layer, the water vapor transmission rate measured according to the JISK7129B method is 10 ⁻⁴ g / m ² / day or less, preferably 10 ⁻⁵ g / m ² / day or less, and the oxygen transmission rate is 0.00. 01ml ^/ m 2 ^/ day or less, preferably the film is obtained as a base material excellent resin film barrier property or less 0.001ml ^/ m 2 ^/ day.

When the composition ratio of O atoms to Si atoms is close to 2.0, the composition approaches that of SiO ₂ . If SiO ₂ average density (g / cm ³⁾ becomes 2.2. If a composition close to SiO ₂ is formed, a dense structure can be formed and a sufficient barrier property is expected.

  Regarding the ten-point average roughness of the surface of the barrier layer, Rzjis (JIS B 0601: 2001), by converting the layer having a high surface smoothness and a uniform thickness into a barrier layer by coating in advance. The stress concentration at the time of bending can be alleviated, the bending resistance can be increased, the characteristics expected of a flexible film substrate can be met, and roll-to-roll production can be achieved.

  In order to exhibit such characteristics, the ten-point average roughness of the barrier layer surface layer, Rzjis, must not be submicron (0.1 μm = 100 nm) or more, and Rzjis must be 90 nm or less. Furthermore, Rzjis is more preferably 30 nm or less.

  As a means for achieving this, the application of a layer that is converted into a barrier layer with respect to chemical vapor deposition is excellent, and further, it is necessary to produce in an environment with a high degree of cleanliness with little foreign matter. Specifically, it is necessary that the cleanliness is higher than that of class 1000.

  The density of the barrier layer of the present invention is a suitable means in that X-ray reflectivity measurement (XRR) is nondestructive and information in the depth direction from the surface can be obtained. However, in order to obtain more accurate information, it is important to measure the composition in the depth direction from the surface in advance, and the composition ratio of O atoms and other atoms to Si atoms is determined by sputtering. It can be quantified by time-of-flight secondary ion mass spectrometry (TOF-SIMS) or X-ray photoelectron spectroscopy (XPS). Usually, XPS is preferably used. A solid X-ray surface is irradiated with soft X-rays and the kinetic energy of photoelectrons emitted from the surface is measured by the photoelectric effect. Since the escape depth of the photoelectrons is several nm, information on atoms and molecules constituting a layer close to the outermost surface of the solid can be obtained. By using sputtering by ion (Ar, Xe) irradiation in combination, information such as composition from the surface in the depth direction and changes in the bonding state can be obtained. In the depth direction of the barrier layer, the composition is analyzed by sputtering at regular intervals up to the thickness depth to the surface in contact with the barrier layer and the substrate side, starting from the outermost surface where there is no dirt or foreign matter attached. . The measurement interval is 1 nm interval or more and 50 nm or less, and preferably 2 nm or more and 30 nm or less. When the thickness of the barrier layer is different from an integral multiple of the measurement interval, the nearest integer multiple of the measurement location that is equal to or less than the barrier layer thickness is taken as the end point of the composition comparison.

  In particular, the water vapor permeability of the barrier film of the present invention is such that when used as a substrate of an organic photoelectric conversion element, if a base material with poor barrier properties is used, water vapor or air penetrates and the performance is likely to deteriorate over time. There is a problem of becoming. In addition, when used in applications that require high water vapor barrier properties such as organic EL displays and high-definition color liquid crystal displays, especially in the case of organic EL display applications, a growing dark spot occurs. Since the display life of the display may become extremely short, the water vapor permeability measured according to the JISK7129B method is preferably not more than the above value.

  In order to achieve such barrier properties, it is preferable that the 10-point average roughness, Rzjis, of the barrier layer surface layer is 1 nm or more and 30 nm or less. The barrier film of this invention can obtain a barrier layer smoother than the surface of a smooth layer by apply | coating a silicon compound on a smooth layer, and forming a ceramic layer. Thereby, when used for various device elements, bending resistance can be improved.

Barrier Layer Formation Method The barrier layer formation method of the present invention includes a coating solution containing at least one silicon compound on a base material, and then reforming treatment in an oxidizing gas atmosphere (conversion to a barrier layer). And a method of forming a barrier layer containing silicon oxide.

  Any appropriate method can be adopted as a coating method. Specific examples include a spin coating method, 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 20 nm to 100 μm, more preferably about 20 nm to 10 μm, and most preferably about 20 nm to 1 μm.

  Next, it is preferable to anneal the applied film. The annealing temperature is preferably 60 ° C to 200 ° C, more preferably 70 ° C to 160 ° C. The annealing time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 2 hours. By performing annealing in such a range, a part of polysilazane reacts to immobilize molecules, and a barrier film having good characteristics can be obtained. Specifically, it is assumed that molecules are immobilized by the following mechanism. The annealing may be performed at a constant temperature, the temperature may be changed stepwise, or the temperature may be continuously changed (temperature increase and / or temperature decrease). During annealing, it is preferable to adjust the humidity in order to stabilize the reaction, and is usually 1% RH to 90% RH, more preferably 5% RH to 70% RH.

  The supply of the silicon compound for forming the silicon oxide barrier layer is more uniform and smoother when applied to the surface of the barrier film substrate than when supplied as a gas as in CVD. Can do. It is well known that in the case of a CVD method, foreign substances called unnecessary particles are generated in the gas phase simultaneously with the step of the volume of the source material having increased reactivity in the gas phase on the substrate surface. By preventing the raw material from being present in the plasma reaction space, the generation of these particles can be suppressed. This is excellent in terms of dark spot suppression and bending resistance improvement described above.

  Preferred silicon compounds that can be used in the present invention include perhydropolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, and dimethyldiethoxysilane. , Methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane , Dimethyldivinylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsila 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyltrimethoxysilane, methyltrivinylsilane, Diacetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, tetraacetoxysilane, 3-trifluoroacetoxypropyltrimethoxy Silane, diaryldimethoxysilane, butyldimethoxyvinylsilane, trimethyl-3-vinylthiopropylsilane Phenyltrimethylsilane, dimethoxymethylphenylsilane, phenyltrimethoxysilane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3- Glycidoxypropyltrimethoxysilane, 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxypropyldimethoxymethylsilane , 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glyci Doxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, Divinylmethylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolylvinylsilane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3- Glycidoxypropylmethylsilane, octyloxytrimethylsilane, phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylpheny Silane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, diaryldiphenylsilane, octadecyltrimethylsilane, methyloctadecyldimethylsilane, docosylmethyldimethylsilane, 1,3-divinyl-1,1,1 3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) ) Tetramethyldisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5 -Trimethylcyclotrisiloxane, octamethylcyclote La siloxane, 1,3,5,7-tetra-ethoxy-1,3,5,7-tetramethyl cyclotetrasiloxane, may be mentioned decamethylcyclopentasiloxane like.

  Of these, silicon compounds that are solid at room temperature are preferable, and perhydropolysilazane, silsesquioxane, and the like are more preferably used. In order to promote the conversion to a silicon oxide compound, an amine or metal catalyst may be added. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials. When these are applied, in order to suppress the reaction between the coating solution and moisture, it is preferable to use a solvent that does not easily contain moisture, such as xylene, dibutyl ether, solvesso, turpentine, and the like.

  The silsesquioxane, Mayaterials manufactured by Q8 series of Octakis (tetramethylammonium) pentacyclo-octasiloxane-octakis (yloxide) hydrate; Octa (tetramethylammonium) silsesquioxane, Octakis (dimethylsiloxy) octasilsesquioxane, Octa [[3 - [(3-ethyl- 3-oxetylyl) methoxy] propyl] dimethylsiloxy] octasilsesquioxane; Octalyloxetanes sesquioxane, Octa [(3-Propylglycidyletherer) d methylsiloxy] silsesquioxane; Octakis [[3- (2,3-epoxypropoxy) propyl] dimethylsiloxy] octasilsesquioxane, Octakis [[2- (3,4-epoxycyclohexyl) ethyl] dimethylsiloxy] octasilsesquioxane, Octakis [2- (vinyl) dimethylsiloxy] silsesquioxane Octakis (dimethylvinylsilyloxy) octasilsesquioxane, Octakis [(3-hydroxypropylo) dimethylsiloxyxy, octasilsequioxane, Octa [( methacryloylpropyl) dimethylsilyloxy] silsesquioxane octakis [(3-methacryloxypropyl) dimethylsiloxy] octasylsequioxane, and compounds of the following structural formula.

  For example, heat treatment (400 to 500 ° C.) is known as another method for converting a silicon compound into a silicon oxide compound other than those described above. However, unlike glass substrates and silicon wafers, the roll-to-roll production of the present invention is possible. In the case of a film substrate such as transparent plastic, it was not applicable from the viewpoint of heat resistance. It may be applicable to some special engineering plastic films, but these are more expensive than general-purpose plastic films, and there are problems such as the inability to obtain colorlessness / transparency. It was. The reason why it is difficult to obtain colorlessness / transparency of such a heat-resistant plastic is generally attributed to the fact that a double bond conjugated system represented by an aromatic bond has visible light absorption. A typical example of such a film is polyimide (PI).

In order to improve this point, various catalysts for lowering the conversion temperature have been studied. However, the catalyst remaining in the coating film has a disadvantage that the barrier property and transparency are lowered. Further, UV ozone treatment is known as a surface treatment instead of heat treatment. However, none of the techniques has a sufficient function as a barrier layer, and the barrier property such that the water vapor transmission rate is significantly lower than 1 × 10 ⁻² g / m ² · day has not been obtained.

  The barrier layer of the present invention may be a single layer or a plurality of similar layers, and the barrier properties can be further improved by a plurality of layers.

<Pretreatment for reforming treatment>
Depending on the configuration and manufacturing process, oxygen source such as moisture and oxygen may be present on the surface of the polysilazane coating layer before the modification treatment (processing to convert to a barrier layer) and the stress relaxation layer adjacent to the polysilazane coating layer or in the layer. There are many.

  As a final form, the gas barrier film is used for the element. At this time, since moisture or oxygen contained in the gas barrier film itself is an inhibitor of the element, a vacuum is used as a pretreatment before the reforming process. It is preferable to perform a treatment / heat vacuum treatment to remove excess moisture, oxygen, and the like. It is difficult to remove moisture and oxygen trapped in the gas barrier film after improving the gas barrier properties after the reforming treatment, because the removal treatment of moisture and oxygen at this timing is useful in the process. Because it becomes.

<Reforming treatment>
As the oxidation treatment of polysilazane, steam oxidation and / or heat treatment (including drying treatment), treatment by ultraviolet irradiation, and the like are known.

  In the present invention, plasma treatment and vacuum ultraviolet treatment are recommended as particularly effective modification treatment methods.

Plasma Treatment The plasma treatment used in the present invention performs plasma discharge treatment while supplying a discharge gas that tends to be in a plasma state without supplying raw materials in the case of a plasma CVD method described later.

  By supplying oxygen having an oxidizing property as the reaction gas, the oxidation reaction can be advanced. As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost. Specifically, it is described in International Publication No. 2007/026545.

  The international publication discloses that two or more electric fields having different frequencies are applied to the discharge space, and an electric field obtained by superimposing the first high-frequency electric field and the second high-frequency electric field is applied. The method is preferred.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge start The relationship with the electric field strength IV is
V1 ≧ IV> V2 or V1> IV ≧ V2
And the output density of the second high-frequency electric field is 1 W / cm ² or more.

  By taking such a discharge condition, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. I can do it.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is possible to increase the plasma density by a high power density and form a dense and high-quality thin film.

  It must be transparent as a final form. That is, in order to obtain a barrier film having a high barrier property characterized by having a visible light transmittance of 400 to 800 nm of 70% or more and 90% or less, a dense barrier layer convertible layer at a low temperature on a transparent plastic film. As the processing (conversion) method, the two-frequency AGP processing using the first and second high-frequency electric fields is excellent in the plasma processing. AGP treatment refers to chemical vapor deposition, that is, physical deposition using a source gas as at least one of the reaction gases, whereas surface modification by applying atmospheric pressure plasma energy, in this application to the barrier layer It means conversion process.

Vacuum ultraviolet treatment As a method for converting (modifying) the barrier layer, there is a vacuum ultraviolet treatment (vacuum ultraviolet irradiation treatment) as an effective method other than the two-frequency AGP treatment.

  In the ultraviolet treatment, active oxygen and ozone are generated by irradiating ultraviolet light in the presence of oxygen, and the oxidation reaction can be further advanced.

  This active oxygen and ozone are very reactive.For example, when polysilazane is selected as the silicon compound, the polysilazane coating film that is a precursor of silicon oxide is directly oxidized without passing through silanol. A silicon oxide film with higher density and fewer defects is formed.

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

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

As the light source, a low-pressure mercury lamp, a deuterium lamp, a Xe excimer lamp, a metal halide lamp, an excimer laser, or the like can be used. As the output of the lamp 400W～30kW, more preferably preferably ^{10mJ / cm 2 ~5000mJ / cm 2} , 100mJ / cm 2 ~2000mJ / cm 2 as ^{100mW / cm 2 ~100kW / cm 2} , irradiation energy as illuminance . Moreover, the illuminance at the time of ultraviolet irradiation is preferably 1 mW / cm ^{2 to} 10 W / cm ² . By irradiating the polysilazane coating film with ultraviolet rays in an oxidizing gas atmosphere, the polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. Control is possible by irradiation time and wavelength (energy density of light), and it is possible to select appropriately such as properly using different types of lamps in order to obtain a desired film structure. Further, not only m ² which is continuously irradiated but also a plurality of times of irradiation may be performed, and the plurality of times of irradiation may be so-called pulse irradiation in a short time.

  In addition, heating the coating film simultaneously with ultraviolet irradiation is also preferably used to promote a reaction (also referred to as an oxidation reaction or a conversion treatment). The heating method is a method of heating a coating film by contacting a base material with a heating element such as a heat block, a method of heating an atmosphere with an external heater such as a resistance wire, and an infrared region light such as an IR heater. There are no particular limitations on the method. You may select suitably the method which can maintain the smoothness of a coating film.

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

  Among them, it is preferable to perform the treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 180 nm or less having a higher photon energy. This is because when the energy is small, the effect of polysilazane is insufficient and the gas barrier property is lowered.

<Treatment by irradiation with vacuum ultraviolet rays having a wavelength component of 180 nm or less>
In the present invention, a preferable method includes a modification treatment by irradiation with vacuum ultraviolet rays. The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 180 nm, which is larger than the interatomic bonding force in the compound, and the oxidation reaction by active oxygen or ozone while directly cleaving the bonds of atoms by the action of only photons called photon processes. Is a method of forming a film at a relatively low temperature.

  As the vacuum ultraviolet light source necessary for the above, a rare gas excimer lamp is preferably used.

1. Excimer light emission is called an inert gas because atoms of rare gases such as Xe, Kr, Ar, and Ne do not form a molecule by chemically bonding. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. In addition, since the luminous efficiency is higher than that of other rare gases and a lamp for irradiating a large area can be made of quartz glass, a Xe excimer lamp can be preferably used.

  From the standpoint of energy alone, Ar excimer light (wavelength 126 nm) is the highest, and a high polysilazane layer reforming effect is expected. However, since Ar excimer light becomes so large that absorption by quartz glass cannot be ignored, it is necessary to use calcium carbonate glass instead of silicon dioxide glass. However, the fact is that calcium carbonate glass is very fragile and difficult to manufacture as a lamp that irradiates a large area.

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

  According to the study by the present inventors, the oxygen concentration is preferably 0.001 to 5% as the environment during the excimer irradiation treatment. Furthermore, if it is 0.01 to 3%, performance is stable and preferable. When the oxygen concentration exceeds 5%, energy is consumed to generate active oxygen, etc., rather than bond breakage. Even if the oxygen concentration is reduced to 0.001% or less, the excimer light irradiation efficiency hardly changes, and modification Since the efficiency and the composition controllability of the film do not change, an extra atmosphere replacement time is required, so that it is difficult to improve productivity. Further, it is preferable to apply heat to the stage temperature because the reaction is further accelerated. In this case, the temperature is preferably 50 ° C. or more and Tg + 80 ° C. or less of the base material, and the base material Tg + 30 ° C. or less is more preferable because the reactivity is improved without damaging the base material.

  In principle, it is possible to obtain a thick gas barrier layer from a coating film formed by a single application by irradiating a film applied to a relatively thick film for a long time, but the thick film generates defects. Gas barrier function is difficult to develop. On the contrary, even if it is too thin, a sufficient gas barrier function is not exhibited. Accordingly, as described above, the thickness of the polysilazane is preferably 30 nm to 1000 nm, more preferably 30 nm to 500 nm, still more preferably 30 nm to 300 nm, and particularly 30 nm to 150 nm. Turn into.

  In order to enhance the gas barrier function, a gas barrier layer may be laminated, specifically, a series of steps of polysilazane coating and modification treatment may be repeated.

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

Therefore, in this invention, it is preferable to perform the modification process which gives the maximum irradiation intensity of 100 to 200 mW / cm ² at least once in the vacuum ultraviolet irradiation process. By setting it to 100 mW / cm ² or more, the processing time can be shortened without causing rapid deterioration of the reforming efficiency, and by setting it to 200 mW / cm ² or less, gas barrier performance can be efficiently provided. (Even if irradiation exceeds 200 mW / cm ² , the increase in gas barrier properties slows down), not only damage to the substrate, but also damage to the lamp and other members of the lamp unit can be suppressed. The service life can be extended.

<Vacuum ultraviolet irradiation time>
Although the irradiation time can be arbitrarily set, the irradiation time in the high illuminance process is preferably 0.1 second to 3 minutes from the viewpoint of substrate damage and film defect generation and from the viewpoint of reducing variation in gas barrier performance. More preferably, it is 0.5 second to 1 minute.

<Oxygen concentration during vacuum ultraviolet light irradiation>
In the present invention, the oxygen concentration at the time of irradiation with vacuum ultraviolet light is preferably 10 ppm to 50000 ppm (5%). More preferably, it is 1000 ppm to 30000 ppm (3%). If the oxygen concentration is higher than the above concentration range, a gas barrier film containing excessive oxygen is formed, and the gas barrier property is deteriorated. If the oxygen concentration is lower than the above range, the replacement time with the atmosphere will be longer and the productivity will be reduced.At the same time, if continuous production such as roll-to-roll is performed, the web will be transported into the vacuum ultraviolet irradiation chamber. The amount of air to be entrained (including oxygen) increases, and the oxygen concentration cannot be adjusted unless a large flow rate of gas is passed.

  According to the inventors' investigation, in the polysilazane-containing coating film, oxygen and a small amount of water are mixed when applied in the atmosphere, and there are also adsorbed oxygen and adsorbed water on the support other than the coating film, It has been found that there are enough oxygen sources to supply oxygen required for the reforming reaction without introducing oxygen into the irradiation chamber. Rather, when irradiation with vacuum ultraviolet light is performed in an atmosphere containing a large amount of oxygen gas (5 to 10% level), the gas barrier film after the modification has an excessive oxygen structure, and the gas barrier properties deteriorate. Further, as described above, the 172 nm vacuum ultraviolet light is absorbed by oxygen and the amount of light at 172 nm reaching the film surface is reduced, thereby reducing the efficiency of the light treatment. That is, at the time of vacuum ultraviolet light irradiation, it is preferable to perform the modification treatment in a state where the vacuum ultraviolet light efficiently reaches the coating film in a state where the oxygen concentration is as low as possible.

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

Substrate Next, the substrate used in the barrier film of the present invention will be described. The substrate of the present invention is preferably a film substrate having a smooth layer, but is not particularly limited as long as it is formed of an organic material capable of holding a barrier layer having a barrier property described later. .

  Specifically, acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), Silsesquioki having an organic-inorganic hybrid structure such as polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, and other resin films. A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having Sun as a basic skeleton, and a resin film formed by laminating two or more layers of the above resin can be used. In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, inorganic layer, In terms of adhesion to the barrier layer, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure can be preferably used. As for the thickness of a base material, about 5-500 micrometers is preferable, More preferably, it is 25-250 micrometers.

  Moreover, it is preferable that the base material which concerns on this invention is transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. is there.

  In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material used in the present invention can be produced by a conventionally known general method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the flow direction of the base material (vertical axis), or A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  Moreover, in the resin film base material which concerns on this invention, you may corona-treat before forming a vapor deposition film.

Further, an anchor coating agent layer may be formed on the surface of the substrate according to the present invention for the purpose of improving the adhesion with the vapor deposition film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, and alkyl titanates. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate 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 to 5 g / m ² (dry state).

Smooth layer The substrate of the present invention preferably has a smooth layer. The smooth layer according to the present invention flattens the rough surface of the transparent resin film substrate on which protrusions and the like exist, or fills irregularities and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the transparent resin film substrate. Provided for flattening. Such a smooth layer is basically formed by curing a photosensitive resin.

  In addition, regarding the bending resistance to be improved in the present application, it is desirable that the barrier layer has a uniform film thickness. This is to relieve stress concentration during bending. From this viewpoint, it is preferable to provide a smooth layer.

  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.

  Examples of reactive monomers 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, and 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, dicyclo Pentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycy 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, tripropylene Glycol 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-to Limethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, Examples thereof include 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 dye 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 method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

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

  Solvents used when forming a smooth layer using a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, α -Or terpenes such as β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Group hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropiate Glycol ethers such as lenglycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glycol Alkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the ten-point average roughness and Rzjis are preferably 10 nm or more and 30 nm or less. If the value is smaller than this range, the coatability is impaired when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or wireless bar at the stage of coating a silicon compound described later. There is a case. Moreover, when larger than this range, it may become difficult to smooth the unevenness | corrugation after apply | coating a silicon compound.

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

Additive to smooth layer One of the preferred embodiments is a reactive silica particle (hereinafter, also simply referred to as “reactive silica particle”) in which a photosensitive group having photopolymerization reactivity is introduced on the surface of the photosensitive resin. ). Here, examples of the photopolymerizable photosensitive group include polymerizable unsaturated groups represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.

  Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By setting the average particle size in such a range, the antiglare property and the resolution, which are the effects of the present invention, can be obtained by using in combination with a matting agent composed of inorganic particles having an average particle size of 1 to 10 μm described later. It becomes easy to form a smooth layer having both optical properties satisfying a good balance and hard coat properties. From the viewpoint of making it easier to obtain such an effect, it is more preferable to use an average particle diameter of 0.001 to 0.01 μm. The smooth layer used in the present invention preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. By adding 20% or more, adhesion with the barrier layer is improved. On the other hand, if it exceeds 60%, the film may be bent or cracked when heat-treated, or the optical properties such as transparency and refractive index of the barrier film may be affected.

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

  Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group.

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

  The thickness of the smooth layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer has a high transparency. When the film is provided on only one surface of the molecular film, curling of the smooth film can be easily suppressed.

Bleed-out prevention layer When the film having a smooth layer is heated, the barrier film of the present invention suppresses the phenomenon that unreacted oligomers migrate from the film substrate to the surface and contaminate the contact surface. For this purpose, it is preferable to provide a bleed-out preventing layer on the opposite surface of the substrate having the smooth layer.

  The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

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

  Examples of polyunsaturated organic compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, ditrimethylolpropante La (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.

  Examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxy) Ethoxy) ethyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2- Examples include methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. .

  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 part by mass, more preferably not more than 16 parts by mass.

  In addition, the smooth layer of the present invention 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.

  Examples of such thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof. Vinyl resins such as polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonates Examples thereof include resins.

  Moreover, as a thermosetting resin, the thermosetting urethane resin which consists of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, a silicone resin etc. are mentioned.

  Moreover, as ionizing radiation curable resin, it hardens | cures by irradiating ionizing radiation (an ultraviolet ray or an electron beam) to the ionizing radiation hardening coating material which mixed 1 type (s) or 2 or more types, such as a photopolymerizable prepolymer or a photopolymerizable monomer. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.

  As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl) Examples include -1-propane, α-acyloxime ester, and thioxanthone.

  The bleed-out prevention layer as described above is prepared as a coating solution by mixing a hard coat agent, a matting agent, and other components as necessary, and appropriately using a diluent solvent as necessary. It can be formed by coating the material surface with a conventionally known coating method and then curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays having 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 in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the smooth film, and the smooth layer is one of the transparent polymer films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

Layer having a silicon compound The barrier film of the present invention is not limited to the optimum method provided by the above-described application, but includes a sputtering method, an ion assist method, a plasma CVD method described later, an atmospheric pressure described later, or a pressure near atmospheric pressure. It is preferable that a layer having a silicon compound is formed by applying a plasma CVD method or the like. In particular, the method using atmospheric pressure plasma CVD does not require a decompression chamber and can produce a high-speed film. This is preferable because it is a highly reliable film forming method. This is because a barrier layer having a higher barrier property can be easily formed by additionally forming the layer having the silicon compound by plasma CVD.

  The sputtering method, ion assist method, and plasma CVD method can form a film having a high barrier property. On the other hand, fine particles called particles are generated in the film forming process, and defects attached to or on the barrier layer are likely to occur. There is a defect.

  Even if such a defect occurs, the barrier film of the present invention can suppress gas permeation from the defective part due to the presence of the layer having the above-described silicon compound, and can realize higher barrier properties. .

  The thickness of the layer having these silicon compounds in the present invention is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 1 to 2000 nm. This is because when the thickness of the layer having a silicon compound is smaller than the above range, a uniform film cannot be obtained, and it is difficult to improve the gas barrier property. In addition, when the thickness of the layer having a silicon compound is thicker than the above range, it is difficult to maintain the flexibility of the barrier film. This is because cracks may occur.

  If the thickness is less than this, there are many film defects, and sufficient moisture resistance cannot be obtained. The larger the thickness, the higher the moisture resistance theoretically. However, when the thickness is too large, the internal stress becomes unnecessarily large, and it is easy to break, and a preferable moisture resistance cannot be obtained.

  In the present invention, the layer having the silicon compound is preferably transparent. It is because it becomes possible to make a barrier film transparent by being transparent, and it can also be used for uses, such as a transparent substrate of an EL element. As the light transmittance of the barrier film, for example, when the wavelength of the test light is 550 nm, the transmittance is preferably 80% or more, and more preferably 90% or more.

  A layer having a silicon compound obtained by a plasma CVD method or a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure is composed of an organic metal compound, decomposition gas, decomposition temperature, input power, etc. that are raw materials (also referred to as raw materials). By selecting the conditions, ceramic layers such as metal carbides, metal nitrides, metal oxides, metal sulfides, etc., and mixtures thereof (metal oxynitrides, metal nitride carbides, etc.) can be formed separately, which is preferable.

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

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

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

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

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.

  As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

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

  In the layer having a silicon compound according to the present invention, the inorganic compound contained is SiOxCy (x = 1.5 to 2.0, y = 0 to 0.5) or SiOx, SiNy or SiOxNy (x = 1 to 1). 2, y = 0.1-1), and from the viewpoint of light transmittance and suitability for atmospheric pressure plasma CVD described later, SiOx is preferable.

  The inorganic compound contained in the layer having a silicon compound according to the present invention includes, for example, a combination of oxygen gas and nitrogen gas in a predetermined ratio with the above organic silicon compound, and at least one of an O atom and an N atom, an Si atom, Can be obtained.

  As described above, various inorganic thin films can be formed by using the source gas as described above together with the discharge gas.

  Next, the atmospheric pressure plasma CVD method that can be suitably used for forming the layer having a silicon compound according to the present invention in the method for producing a barrier film of the present invention will be described in more detail.

  In CVD (chemical vapor deposition), volatilized and sublimated organometallic compounds adhere to the surface of a high-temperature substrate, causing a thermal decomposition reaction to produce a thermally stable inorganic thin film. In such a normal CVD method (also referred to as a thermal CVD method), a substrate temperature of 500 ° C. or higher is usually required, so that it is difficult to use for forming a film on a plastic substrate. In the CVD method, an electric field is applied to the space in the vicinity of the substrate to generate a space (plasma space) in which a gas in a plasma state exists, and a volatilized and sublimated organometallic compound is introduced into the plasma space to cause a decomposition reaction. Is formed on the substrate to form an inorganic thin film. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions and radicals, so that the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the substrate on which the inorganic material is formed and can sufficiently form the film on the resin film substrate.

  Further, according to this method, a thin film having a stable performance can be obtained with a dense film density when the ceramic layer is formed on the resin film.

  Next, an example of a method for laminating the layer having the silicon compound using a plasma CVD method at or near atmospheric pressure will be described.

  In the plasma discharge treatment apparatus, the source gas containing metal and the decomposition gas are appropriately selected from the gas supply means, and a discharge gas that tends to be in a plasma state is mainly mixed with these reactive gases. The above layer can be obtained by feeding a gas into the plasma discharge generator.

  As the discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as described above. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

  As an atmospheric pressure plasma discharge treatment apparatus applicable to the present invention, for example, atmospheric pressure plasma discharge treatment described in JP-A No. 2004-68143, No. 2003-49272, WO 02/48428, etc. An apparatus can be mentioned.

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

  The gas barrier film of the present invention can be particularly useful for photoelectric conversion elements and EL elements. Since the gas barrier film of the present invention is transparent, when this gas barrier film is used as a support for a photoelectric conversion element, it can be configured to receive sunlight from this side, and when used for an EL element, Light emission efficiency is not deteriorated because light emission from the element is not hindered.

  The barrier film of the present invention can be used for an organic photoelectric conversion element, for example. Since the barrier film of the present invention is transparent when used in an organic photoelectric conversion element, it can be configured to receive sunlight from this side using this barrier film as a base material. That is, on this barrier film, for example, a transparent conductive thin film such as ITO can be provided as a transparent electrode to constitute a resin substrate for organic photoelectric conversion elements. Then, an ITO transparent conductive film provided on the substrate 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 stopper material (although it may be the same), bonding the barrier film substrate and the periphery, and encapsulating the element, thereby allowing the element to use moisture such as ambient air or oxygen Can seal the impact on

  The resin base material for organic photoelectric conversion elements is obtained by forming a transparent conductive film on the ceramic layer of the barrier film thus formed. 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.

  As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 nm to 1000 nm is preferable.

  Subsequently, the organic photoelectric conversion element using these barrier films and the resin base material for organic photoelectric conversion elements in which the transparent conductive film was formed in this is demonstrated.

[Sealing film and manufacturing method thereof]
The present invention is characterized in that a barrier film having the ceramic layer is used as a substrate.

  In the barrier film having the ceramic layer, a transparent conductive film is further formed on the ceramic layer, and the layer constituting the organic photoelectric conversion element and the layer serving as the cathode are stacked thereon using the transparent conductive film as an anode. Further, another barrier film is used as a sealing film to be sealed by overlapping.

  As another sealing material (sealing film) used, a barrier film having a ceramic layer having the dense structure according to the present invention can be used. Also, for example, known barrier films used for packaging materials, such as plastic films deposited with silicon oxide or aluminum oxide, dense ceramic layers, and flexible impact relaxation polymer layers are laminated alternately A barrier film having the structure described above can be used as the sealing film. In particular, a resin-laminated (polymer film) metal foil cannot be used as a barrier film on the light extraction side, but it is a low-cost and further low-moisture-permeable sealing material and does not intend to extract light (with transparency). When not required), it is preferable as a sealing film.

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

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

  The thickness of the metal foil is preferably 6 to 50 μm. If the thickness is less than 6 μm, depending on the material used for the metal foil, pinholes may be vacant during use, and required barrier properties (moisture permeability, oxygen permeability) may not be obtained. If it exceeds 50 μm, the cost may increase depending on the material used for the metal foil, and the merit of the film may be reduced because the organic photoelectric conversion element becomes thick.

  As a resin film in a metal foil laminated with a resin film (polymer film), various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin , Polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, vinylidene chloride Based resins and the like. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. In addition, a polyethylene resin having a low density or a high density can be used.

  As will be described later, as a method for sealing the two films, for example, a method of laminating a commonly used impulse sealer heat-fusible resin layer, fusing with an impulse sealer, and sealing is preferable. In the sealing between barrier films, if the film thickness exceeds 300 μm, the handling of the film during the sealing operation deteriorates, and it becomes difficult to heat-seal with an impulse sealer or the like, so the film thickness is 300 μm or less. desirable.

[Encapsulation of organic photoelectric conversion elements]
In this invention, after forming a transparent conductive film on the resin film (barrier film) which has the said ceramic layer based on this invention, and forming each layer of an organic photoelectric conversion element on the produced resin base material for organic photoelectric conversion elements The organic photoelectric conversion element can be sealed using the sealing film so as to cover the cathode surface with the sealing film in an environment purged with an inert gas.

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

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

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

  As an adhesion method, the dry laminating method is excellent in terms of workability. This method generally uses a curable adhesive layer of about 1.0 to 2.5 μm. However, when the coating amount of the adhesive is too large, tunneling, oozing, crimping, etc. may occur, so the amount of the adhesive is preferably adjusted to 3 to 5 μm in dry film thickness. It is preferable.

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

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

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

  Next, 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)
Although the preferable aspect of the organic photoelectric conversion element which concerns on this invention is demonstrated, it is not limited to this. There is no restriction | limiting in particular as an organic photoelectric conversion element, The anode and the cathode, and the electric power generation layer (a layer in which p-type semiconductor and n-type semiconductor are mixed, a bulk heterojunction layer, i layer) sandwiched between them are at least one layer. 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 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 light emitting layer / electron transport layer / intermediate electrode / hole transport layer / second light emitting layer 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, which are substantially two layers and heterojunction. Alternatively, a bulk heterojunction that is in a mixed state in one layer may be formed, 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). It may be a configuration (also referred to as a pin configuration). Moreover, in order to improve the utilization efficiency of sunlight, the tandem configuration (configuration (v)) in which sunlight of different wavelengths is absorbed by each power generation layer may be employed.

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

  Furthermore, the preferable aspect of the organic photoelectric conversion element which concerns on detailed this invention is demonstrated below.

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

  The substrate 11 is a member that holds the anode 12, the power generation layer 14, and the cathode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction organic photoelectric conversion element 10 may be configured by forming the anode 12 and the cathode 13 on both surfaces of the power generation layer 14.

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

  In FIG. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

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

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

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

  Below, the material which comprises these layers is described.

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

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zeslen, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, 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-mentioned condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A. 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 described in WO 2008/000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO 2008/000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007 p4160, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., 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, not polymer materials, include thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable.

  Further, 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. Alternatively, a soluble substituent reacts and becomes insoluble (pigmented) 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. Materials etc. can be mentioned.

n-type semiconductor material Although it does not specifically limit as an n-type semiconductor material used for the bulk heterojunction layer of the organic photoelectric conversion element which concerns on this invention, For example, the hydrogen atom of p-type semiconductors, such as fullerene and octaazaporphyrin, is used as a fluorine atom Aromatic carboxylic acid anhydrides such as substituted perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide, Examples thereof include a polymer compound containing the imidized product as a skeleton.

  However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (˜50 fs) and efficiently 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. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.

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

Hole Transport Layer / Electron Blocking Layer In the organic photoelectric conversion device 10 of the present invention, the hole transport layer 17 is located between the bulk heterojunction layer and the anode, and charges generated in the bulk heterojunction layer can be taken out more efficiently. Since it becomes possible, it is preferable to have these layers.

  As a material constituting these layers, for example, as the hole transport layer 17, PEDOT such as trade name BaytronP, polyaniline and its doped material, cyan compounds described in WO2006 / 019270, etc. 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. It has an electronic block function. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. A layer made of a single p-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

Electron Transport Layer / Hole Blocking Layer The organic photoelectric conversion element 10 of the present invention forms the electron transport layer 18 between the bulk heterojunction layer and the cathode, thereby more efficiently generating charges generated in the bulk heterojunction layer. Since it can be taken out, it is preferable to have these layers.

  As the electron transport layer 18, octaazaporphyrin, a p-type semiconductor perfluoro product (perfluoropentacene, perfluorophthalocyanine, etc.) can be used. Similarly, a p-type semiconductor material used for a bulk heterojunction layer is used. The electron transport layer having a HOMO level deeper than the HOMO level is given a hole blocking function having a rectifying effect so that holes generated in the bulk heterojunction layer do not flow to the cathode side. Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function. Examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide. N-type inorganic oxides such as zinc oxide and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used. A layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

Other Layers For the purpose of improving energy conversion efficiency and device life, various intermediate layers may be included in the device. 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 cathode and anode of the transparent electrode of the organic photoelectric conversion device according to the present invention are not particularly limited and can be selected depending on the device configuration, but preferably the transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.

  Also, a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. A functional polymer 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 of the organic photoelectric conversion element according to the present invention may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination. As the conductive material of the counter electrode, a material having a small work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The counter electrode can be produced by forming a thin film 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 is absorbed again by the photoelectric conversion layer, and more photoelectric conversion efficiency Is preferable.

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

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

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

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating, and with such a configuration, the process of forming one layer This is preferable because it can be omitted.

Metal nanowires As the conductive fibers according to the present invention, organic fibers and inorganic fibers coated with metal, conductive metal oxide fibers, metal nanowires, carbon fibers, carbon nanotubes, and the like can be used. Metal nanowires are preferred.

  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.

  The metal nanowire according to the present invention preferably has an average length of 3 μm or more in order to form a long conductive path with a single metal nanowire and to exhibit appropriate light scattering properties. 3-500 micrometers is preferable and it is especially preferable that it is 3-300 micrometers. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, it is preferable that an average diameter is small from a transparency viewpoint, On the other hand, the larger one is preferable from an electroconductive viewpoint. In this invention, 10-300 nm is preferable as an average diameter of metal nanowire, and it is more preferable that it is 30-200 nm. In addition, the relative standard deviation of the diameter is preferably 20% or less.

  There is no restriction | limiting in particular as a metal composition of the metal nanowire which concerns on this invention, Although it can comprise from the 1 type or several metal of a noble metal element and a base metal element, noble metals (for example, gold, platinum, silver, palladium, rhodium, (Iridium, ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin is preferable, and at least silver is more preferable from the viewpoint of conductivity. In order to achieve both conductivity and stability (sulfurization and oxidation resistance of metal nanowires and migration resistance), it is also preferable to include silver and at least one metal belonging to a noble metal other than silver. When the metal nanowire according to the present invention includes two or more kinds of metal elements, for example, the metal composition may be different between the inside and the surface of the metal nanowire, or the entire metal nanowire has the same metal composition. May be.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas phase method can be used. Moreover, there is no restriction | limiting in particular in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. , 2002, 14, 4736-4745, etc. As a method for producing Co nanowires, a method for producing Au nanowires is disclosed in JP 2006-233252A, and a method for producing Cu nanowires is disclosed in JP 2002-266007 A, etc. Reference can be made to Japanese Unexamined Patent Publication No. 2004-149871. In particular, Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in (1) can be easily produced in an aqueous system, and since the conductivity of silver is the highest among metals, it is preferable as the method for producing metal nanowires according to the present invention. Can be applied.

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

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

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

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

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

  Examples of the light scattering 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 Formation method of various layers Bulk heterojunction layer in which electron acceptor and electron donor are mixed, and formation method of transport layer / electrode include vapor deposition method, coating method (cast method, spin method) (Including a coating method). Among these, examples of the method for forming the bulk heterojunction layer include a vapor deposition method and a coating method (including a casting method and a spin coating method). Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. The coating method is also 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 casting method from a solution, a dip coat method, a blade coat method, a wire bar coat method, a gravure coat method, a spray coat method etc. are mentioned. Furthermore, patterning can also be performed by a printing method such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, or a flexographic printing method.

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

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

Patterning There is no restriction | limiting in particular in the method and process of patterning the electrode, electric power generation layer, positive hole transport layer, electron transport layer, etc. which concern on this invention, A well-known method can be applied suitably.

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

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

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

Example 1
A barrier film (sample) was prepared / evaluated as shown below.

(Base material)
As a base material of the thermoplastic resin, a substrate of a polyester film (Tetron O3, manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 125 μm that is easily bonded on both surfaces was annealed at 170 ° C. for 30 minutes.

(Preparation of a film having a smooth layer and a bleed-out prevention layer)
By the following forming method, a bleed-out prevention layer was formed on one side, and a smooth layer was formed on the opposite side to obtain a barrier film substrate.

(Formation of bleed-out prevention layer)
A UV curing type organic / inorganic hybrid hard coating material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the above base material, applied with a wire bar so that the film thickness after drying was 4 μm, and then curing conditions: 1.0 J / cm ² under air, a high pressure mercury lamp used, drying conditions; 80 ° C., subjected to cure for 3 minutes to form a bleedout-preventing layer.

(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the substrate, and the film was coated with a wire bar so that the film thickness after drying was 4 μm, followed by drying conditions; After drying at 80 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions; 1.0 J / cm ² curing was performed to form a smooth layer.

  The ten-point average roughness and Rzjis at this time were 16 nm.

  The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.

(Preparation of barrier film sample No. 1-1)
(Formation of barrier layer)
Next, a ceramic layer was formed on the sample provided with the smooth layer and the bleed-out prevention layer under the following conditions.

[Ceramic layer coating solution]
Perhydroxypolysilazane (PHPS) (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) 20% by mass dibutyl ether solution Using a wireless bar, the film thickness after drying was applied to 0.3 μm and dried. A sample was obtained. The applied film was annealed by treatment for 30 minutes in an atmosphere at a temperature of 80 ° C. and a humidity of 40% RH.

[Heat treatment]
Further, a barrier layer was formed by treatment at 450 ° C. for 1 hour in an oven. 1-1 was obtained. Sample No. 1-1 cracked the barrier layer.

(Preparation of barrier film sample Nos. 1-2 to 1-10, 2-1 to 2-8, 3-1, 3-2 and 4-1 to 4-3)
Sample No. 1 was changed in the same manner as Sample 1-1 except that the base material of Sample 1-1 was changed to that of Table 1 and the coating solution and the processing method were changed as shown in Table 1. 1-2 to 1-10, 2-1 to 2-8, 3-1, 3-2, and 4-1 to 4-3 were obtained. In Table 1, the amine compound used in the coating solution containing an amine catalyst is NAXCAT-10DB manufactured by AZ Electronic Materials.

  The base material of Sample 2-1 is a 125 μm thick PEN with a 125 μm thick polyethylene naphthalate (Teonex Q83, manufactured by Teijin DuPont Films Co., Ltd.) that is easily bonded on both sides, and annealed at 170 ° C. for 30 minutes. What was heat-processed was used.

  Furthermore, as a difference in film thickness of PET, 75 μm is a substrate of polyester film (Tetron O3, manufactured by Teijin DuPont Films Co., Ltd.) that is easily bonded on both surfaces, and annealed at 170 ° C. for 30 minutes, 38 μm. Used is a polyester film substrate (Tetron HS, manufactured by Teijin DuPont Films, Ltd.) that has been subjected to an easy-adhesion process on both sides, and annealed at 170 ° C. for 30 minutes.

  Moreover, the ceramic layer coating liquid of Sample 2-2 was a 20% by mass dibutyl ether solution (without amine catalyst) of perhydroxypolysilazane (PHPS) (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) This is a coating solution in which a 20% by weight dibutyl ether solution (containing 5% by weight of an amine catalyst) of perhydroxypolysilazane (PHPS) (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) is mixed at a ratio of 4: 1.

  In Sample 2-6, a 5% toluene (described as Silsesquioxane in Table 1) solution of octa (hydrodimethylsiloxy) silsesquioxane in a wireless bar was used, and the film thickness after drying was 0.3 μm. It was applied and dried so that

[UV ozone treatment]
The treatment method for Sample 1-7 is a UV ozone treatment for 12 hours while heating to 90 ° C. The conditions were implemented using a UV ozone generator UV253HR12 (low pressure mercury lamp: synthetic quartz, wavelengths 184.9 nm, 253.7 nm) manufactured by Philgen Co., Ltd., with a maximum output of 1500 VA (= W).

[2 layers of barrier layers]
For Samples 3-1, 3-2 and 4-14-2, the polysilazane coating to AGP treatment was repeated twice in the same manner to perform two-layer lamination of the barrier layer. Alternatively, a CVD barrier layer was laminated on a barrier layer formed by applying polysilazane to AGP. The detailed conditions for forming the CVD barrier layer were the same as those of the following plasma-processed two-frequency AGP barrier.

[Plasma treatment]
Samples 1-8 to 1-10, 2-1 to 2-6, 3-1, 3-2, 4-1, and 4-2 were subjected to plasma treatment under the following conditions to form barrier layers. The substrate holding temperature during the formation of the barrier layer was 120 ° C.

  Processing is performed using a roll electrode type discharge treatment device. A plurality of rod-shaped electrodes opposed to the roll electrode were installed in parallel to the film transport direction, and raw materials and electric power were supplied to each electrode portion, and the coated surface was plasma-treated as follows.

  Here, the dielectric body was coated with 1 mm of a single-walled ceramic sprayed one with both opposing electrodes. The electrode gap after coating was set to 1 mm. The metal base material coated with a dielectric has a stainless steel jacket specification having a cooling function by cooling water, and was performed while controlling the electrode temperature by cooling water during discharge. The power source used here was a high-frequency power source (80, 100 kHz) manufactured by Applied Electronics, or a high-frequency power source (13.56 MHz) manufactured by Pearl Industry.

[Dual frequency AGP barrier (CVD barrier layer stacking conditions are the same)]
Discharge gas: N ₂ gas Reaction gas 1: 8% of oxygen gas with respect to the total gas
Reaction gas 2: TEOS is 0.1% of the total gas
Low frequency side power supply power: 100 kHz 2 W / cm ²
High frequency side power supply power: 13.56 MHz at 10 W / cm ²
[Dual frequency oxygen AGP treatment]
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ²
High frequency side power supply power: 13.56 MHz at 9 W / cm ²
[Single-frequency oxygen AGP treatment 1]
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
Low frequency side power supply power: 80 kHz, 3 W / cm ²
[Single-frequency oxygen AGP treatment 2]
Discharge gas: N ₂ gas Reaction gas: 7% of oxygen gas to the total gas
High frequency side power supply power: 13.56 MHz at 9 W / cm ²
[Excimer treatment]
Samples 2-7, 2-8, and 4-3 were subjected to excimer treatment under the following conditions to form a barrier layer. For 4-3, polysilazane coating to excimer treatment was repeated twice in the same manner to carry out two-layer lamination of a barrier layer.

  Using a stage movable xenon excimer irradiation device MODEL: MECL-M-1-200 manufactured by MD Excimer, the stage moving speed is controlled while controlling the atmosphere in the irradiation chamber using nitrogen and oxygen as follows. The sample was reciprocated at a speed of 5 mm / second and irradiated a total of 10 reciprocations. This apparatus is equipped with one Xe excimer lamp with an effective irradiation width of 10 mm, and corresponds to 1 second processing / pass when transported at a stage transport speed of 10 mm / sec. The film thickness of the gas barrier layer after the modification treatment was 150 nm.

(Excimer processing conditions)
Excimer light intensity: 60 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
(Atmosphere condition of sample 2-7 and stage heating temperature)
10 round trips: 1.5% oxygen concentration Stage heating temperature: 80 ° C
(Atmosphere conditions for sample 2-8)
10 round trips: Oxygen concentration 0.01% Stage heating temperature: 100 ° C
(Atmosphere conditions for sample 4-3)
10 round trips: 0.1% oxygen concentration Stage heating temperature: 120 ° C
[Measurement method of Rzjis after treatment (formation of barrier layer)]
The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is a ten-point average roughness for the amplitude of fine irregularities, measured many times in the section.

[Density measurement method in the depth direction of the barrier layer]
The density in the depth direction of the barrier layer is
It is possible to obtain good and accurate information by performing the two steps of 1) composition analysis in the depth direction and 2) density analysis in the depth direction.

[Composition analysis in depth direction (measurement)]
The barrier film obtained as described above is etched in the depth direction from the surface of the barrier layer (ceramic layer) using a sputtering method, and the outermost surface of the barrier layer is set to 0 nm using an XPS surface analyzer. The atomic composition ratio of the ceramic layer every 10 nm was measured.

  There is no particular limitation on the XPS surface analyzer, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

[Density density analysis (measurement and simulation)]
The density of the barrier layer of the present invention is a suitable means in that X-ray reflectivity measurement (XRR) is nondestructive and information in the depth direction from the surface can be obtained.

  In this example, an X-ray reflectivity measurement (XRR) apparatus manufactured by Rigaku Corporation was used, and density analysis (measurement and simulation) based on the average composition information for every 10 nm in the depth direction obtained in 1). The average value was calculated every 10 nm in the depth direction.

Table 2 shows the average density (g / cm ³ ) from the surface of the barrier layer to 20 nm determined. In Table 2, ○ and ◎ in the evaluation column of density and Rzjis are practical, and × is not practical.

[Measurement method of transmittance (%) of barrier film]
In this example, the visible light transmittance (400 to 800 nm) was measured according to JIS-R-3106.

  The measuring apparatus used was Hitachi spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation, and the visible light transmittance (400 to 800 nm) was classified as follows and listed in Table 2.

○: 70 to 90%
X: Less than 70% Example 2
As shown below, each element (OPV / OLED) was produced / evaluated using the barrier film (sample) of Example 1.

(Organic photoelectric conversion device: production of OPV)
In advance, the barrier film sample No. 1 was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. 1-1 to 1-10, 2-1 to 2-8, 3-1, 3-2, and 4-1 to 4-3 (hereinafter abbreviated as Sample Nos. 1-1 to 4-3) and bending No barrier film sample No. 1-1 to 4-3, indium tin oxide (ITO) transparent conductive film deposited with a thickness of 150 nm (sheet resistance 10 Ω / □) to a width of 2 mm using ordinary photolithography technology and wet etching Patterning was performed to form a first electrode. 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 in chlorobenzene (plectrovirus Toro Nix Co., Ltd. regioregular poly-3-hexylthiophene) and PCBM (manufactured by Frontier Carbon Corporation: 6,6-phenyl _{-C 61} - butyric acid methyl ester) and 3.0 wt% Then, 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 room temperature 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 the vacuum deposition apparatus chamber, the inside of the vacuum deposition apparatus is depressurized to 1 × 10 ⁻⁴ Pa or less, and then the substrate is fed at a deposition rate of 0.01 nm / second. Next, 0.6 nm of lithium fluoride is stacked, and then 100 nm of Al metal is stacked at a deposition rate of 0.2 nm / sec through a shadow mask having a width of 2 mm (vaporization is performed so that the light receiving portion is 2 × 2 mm). Thus, the second electrode was formed. The obtained organic photoelectric conversion element SC-101 was moved to a nitrogen chamber, and sealed using a sealing cap and a UV curable resin to produce an organic photoelectric conversion element having a light receiving portion of 2 × 2 mm size.

(Sealing of organic photoelectric conversion elements)
In an environment purged with nitrogen gas (inert gas), a barrier film sample that was repeatedly bent and a barrier film sample No. 1 that was not bent were arranged with the surface of the two barrier films provided with the barrier layer inside. Two sets of organic photoelectric conversion element sample No. 1 corresponding to each of 1-1 to 4-3. Two sets of organic photoelectric conversion element sample Nos. 1-1 to 4-3 were produced. At the time of sealing, an epoxy photo-curing adhesive is applied as a sealing material to the gas barrier layer, and the organic photoelectric conversion element is sandwiched between the barrier films to be in close contact, and then irradiated with UV light from one side of the substrate. Cured. Thus, the organic photoelectric conversion element sample No. 1-1 to 4-3 were obtained.

(Organic electroluminescence device: Production of OLED)
In advance, the barrier film sample No. 1 was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. 1-1 to 4-3 and the barrier film sample No. which was not bent. In each of 1-1 to 4-3, 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 gas 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 applying the coating solution for forming the hole transport layer, the gas barrier film was subjected to cleaning surface modification 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 gas barrier film 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 base material was put into a decompression chamber and decompressed 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 gas barrier film formed up to the second electrode is moved again to a nitrogen atmosphere, cut into a specified size, and organic electroluminescence element (OLED) sample No. 1-1 to 4-3 were produced.

(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 Element Co., Ltd. was used for the organic EL element thus produced, and a flexible printed substrate (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating).

  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 print base material) was connected using a commercially available roll laminating apparatus, and the organic EL element 101 was manufactured.

  As the sealing member, the same sample Nos. Of the gas barrier film produced in Example 1 were combined with “Yes and No” and “No and No” of repeated bending in the same manner as in OPV. A laminated adhesive (two-component reaction type urethane adhesive) was laminated (adhesive layer thickness 1.5 μm).

  As the adhesive for dry lamination, a composition in which a thermosetting adhesive was uniformly applied to a barrier layer surface with a thickness of 20 μm using a dispenser was used.

  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.

(Evaluation)
<Evaluation of water vapor transmission rate>
The following measurement methods were used for evaluation.

Equipment Vapor deposition equipment: Vacuum vapor deposition equipment JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments.

Raw material Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Preparation of Water Vapor Barrier Evaluation Cell In advance, barrier film sample No. 1 was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm. Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400) on the ceramic layer surface of 1-1 to 4-3, a portion (12 mm × 12 mm) to be vapor-deposited of the barrier film sample before attaching the transparent conductive film is 9 The portion other than the portion was masked, and metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the barrier property before and after bending, a water vapor barrier property evaluation cell was similarly prepared for the barrier film that was not subjected to the bending treatment.

  The obtained sample with both sides sealed is stored at 60 ° C. and 90% RH under high temperature and high humidity, and moisture permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount was calculated and evaluated according to the following evaluation criteria.

  In addition, in order to confirm that there is no permeation of water vapor other than from the barrier film surface, instead of the barrier film sample as a comparative sample, a sample in which metallic calcium was vapor-deposited using a quartz glass plate having a thickness of 0.2 mm, The same 60 ° C., 90% RH high temperature and high humidity storage was performed, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

Less than 5: 1 × 10 ⁻⁵ g / m ² / day 4: 1 × 10 ⁻⁵ g / m ² / day or more, less than 1 × 10 ⁻⁴ g / m ² / day 3: 1 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more The results obtained are shown in the column of water vapor transmission rate in Table 2.

<Organic photoelectric conversion element: Evaluation of durability of OPV>
<Evaluation of energy conversion efficiency>
A barrier film sample that was repeatedly bent as described above and a barrier film sample No. 1 that was not bent. Organic photoelectric conversion element sample No. 1 corresponding to each of 1-1 to 4-3. For 1-1 to 4-3, the solar simulator (AM1.5G filter) was irradiated with light of 100 mW / cm ² intensity, and a mask with an effective area of 4.0 mm ² was superimposed on the light receiving part to evaluate IV characteristics. By measuring the four light receiving portions formed on the same element, the short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF (%) are measured according to the following formula 1. A four-point average value of the obtained energy conversion efficiency PCE (%) was estimated.
(Formula 1) PCE (%) = [Jsc (mA / cm ² ) × Voc (V) × FF (%)] / 100 mW / cm ²
The conversion efficiency as the initial battery characteristics was measured, and the degree of deterioration over time was evaluated by the conversion efficiency remaining rate after the acceleration test stored for 1000 hours in a temperature 60 ° C., humidity 90% RH environment.

  The following evaluation was performed on the ratio of conversion efficiency / initial conversion efficiency after the acceleration test.

5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20% Barrier film sample No. Organic element sample Nos. Corresponding to 1-1 to 4-3, respectively. The evaluation results of 1-1 to 4-3 are shown in the column of the conversion efficiency remaining rate after the acceleration test in Table 2. Incidentally, the barrier film sample No. Organic photoelectric conversion element sample No. 1 corresponding to each of 1-1 to 4-3. In 1-1 to 4-3, no difference was observed in the conversion efficiency remaining rate before and after the acceleration test.

<Organic electroluminescence device: Evaluation of durability of OLED>
<Evaluation of brightness>
A barrier film sample that was repeatedly bent as described above and a barrier film sample No. 1 that was not bent. OLED sample numbers corresponding to 1-1 to 4-3, respectively. For 1-1 to 4-3, the luminance (cd / m ² ) at 100 mW was measured using a spectral radiance meter CS-2000A manufactured by Konica Minolta Sensing Co., Ltd. In addition, the average value of 10-point measurement was calculated | required for evaluation stability.

  The luminance as the initial light emission characteristics was measured, and the degree of deterioration with time was evaluated by the residual luminance rate after the accelerated test stored for 1000 hours in a temperature 60 ° C., humidity 90% RH environment.

  The following evaluation was performed for the ratio of luminance after the acceleration test / initial luminance (luminance residual ratio).

5: 90% or more 4: 70% or more, less than 90% 3: 40% or more, less than 70% 2: 20% or more, less than 40% 1: less than 20% Barrier film sample No. Organic element sample Nos. Corresponding to 1-1 to 4-3, respectively. The evaluation results of 1-1 to 4-3 are shown in the column of OLED after the acceleration test in Table 2. Note that the barrier film sample No. OLED sample numbers corresponding to 1-1 to 4-3, respectively. For 1-1 to 4-3, no difference was observed in the residual luminance ratio before and after the acceleration test.

  As is clear from Tables 1 and 2, the barrier film of the present invention has high visible light transmittance (transparency) and smoothness, and can be produced roll-to-roll (production heat / time load). Furthermore, the organic photoelectric conversion element and the organic electroluminescence element produced by using the barrier film of the present invention are deteriorated in a harsh environment. hard.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode 13 Counter electrode 14 Photoelectric conversion part (bulk hetero junction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion unit 15 charge recombination layer 16 second photoelectric conversion unit 17 hole transport layer 18 electron transport layer 20 photosensor array 21 substrate 22 transparent electrode 23 counter electrode 24 photoelectric conversion part 24a buffer layer 24b photoelectric conversion layer

Claims (8)

A barrier film having a barrier layer containing at least one Si atom and oxygen atom on a substrate, wherein the average density from the surface of the barrier layer to 20 nm is 2.10 g / cm ³ or more and 2.30 g / cm ³ or less, and a barrier film ten-point average roughness of the surface layer of the barrier layer, the Rzjis is equal to or less than 90 nm.   The barrier film according to claim 1, wherein the surface layer of the barrier layer has a ten-point average roughness Rzjis of 30 nm or less.   The barrier film according to claim 1, wherein 1 to 6 barrier layers are further laminated on the barrier layer.   The barrier film according to any one of claims 1 to 3, wherein the base material is polyethylene terephthalate (PET).   The barrier film according to any one of claims 1 to 4, wherein a visible light transmittance at 400 to 800 nm of the barrier film is 70% or more and 90% or less.   An organic photoelectric conversion element or an organic electroluminescence element using the barrier film according to claim 1.   The barrier film according to any one of claims 1 to 5, wherein the barrier film contains a silicon oxide by applying a coating solution containing a silicon compound on a substrate and then subjecting the substrate to a two-frequency plasma treatment in a discharge gas atmosphere. A method for producing a barrier film, which is produced by forming a layer.   The barrier film according to any one of claims 1 to 5, wherein a coating layer containing a silicon compound is applied on a substrate, and then a vacuum ultraviolet ray irradiation treatment is performed to form a barrier layer containing a silicon oxide. A method for producing a barrier film, which is produced by

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