JP2012076385A - Gas barrier film, method of manufacturing gas barrier film, and organic electronic device having the gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which has high gas barrier property, maintains the high gas barrier property even after being bent and has the high stability, to provide a method of manufacturing a gas barrier film which has high productivity and manufactures the gas barrier film inexpensively, and to provide an organic electronic device having the gas barrier film.SOLUTION: The gas barrier film having a first high gas barrier region, a moisture trap region and a second high gas barrier region in this order from a support side has such a gas barrier property that water vapor permeability (water vapor transmission rate:25±0.5°C, relative humidity (90±2)%RH)(WVTR(g/m/day)) measured according to JIS K 7129B method from the support to the first high gas barrier region is 2×10to 1×10, wherein the second high gas barrier region is made of a silicon compound layer, the moisture trap layer is made of a silicon compound layer containing nitrogen atom originated from a silazane compound.

Description

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

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

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

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

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

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

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

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

  In addition, as a method of forming a gas barrier layer by atmospheric pressure plasma that can be formed under atmospheric pressure, not a vapor deposition method that requires a vacuum process, a film forming method capable of stable plasma discharge at a high energy density has also been proposed. (For example, refer to Patent Document 1 and Patent Document 2).

  In the above Patent Documents 1 and 2, in order to prevent cracking when a silica film having a high gas barrier property is formed on a flexible plastic film such as polyethylene terephthalate (PET), A stress relaxation design is performed in which the carbon component is distributed and the hardness of the film decreases toward the base material.

  According to this method, while it is possible to form a high gas barrier film that prevents the occurrence of cracks, it is necessary to carry out film formation at an ultra-low speed in order to obtain a dense barrier film. Have the problem of becoming expensive.

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

  Patent Document 3 discloses a process for converting a polysilazane coating film into a silica film by an oxygen plasma discharge treatment under atmospheric pressure, and a gas barrier layer can be formed without requiring a vacuum process.

However, the water vapor transmission rate of the obtained film is 0.35 g / (m ² · 24 h), which cannot be said to be a gas barrier layer applicable to the device as described above. Generally, it is said that the water vapor transmission rate of a gas barrier layer required for application to an organic photoelectric conversion element needs to be significantly lower than 1 × 10 ⁻² g / (m ² · 24 h).

  On the other hand, Patent Documents 4 and 5 disclose a method of irradiating a polysilazane coating film with ultraviolet rays as a method of forming a dense silica film by converting polysilazane. According to this method, since it is thought that the reaction proceeds by direct oxidation without going through dehydration condensation, silica conversion at a lower temperature becomes possible, and a very effective method for forming a gas barrier layer on a resin film. It can be said.

  However, although Patent Document 4 aims at low-temperature and high-speed formation, it requires 1 minute for ultraviolet irradiation treatment, and further 3 minutes to 2 hours for high-humidity and high-temperature treatment. Therefore, it cannot be said that the formation is sufficiently fast.

Further, in Patent Document 4, it is considered that all the polysilazane coating films are converted to silica, but since they are always combined with high-humidity and high-temperature treatment, a silica conversion film containing a large amount of silanol groups, which can hardly be expected to have a gas barrier property. Is considered the center of the barrier layer configuration. This is also supported by the fact that the water vapor transmission rate of the example is only 6 × 10 ⁻¹ at the best level. Such a water vapor transmission rate of −1 power level cannot be applied as a barrier film for organic electronic devices such as organic photoelectric conversion elements as described above.

  Similarly, Patent Document 5 aims at low temperature formation, but it took 3 hours for ultraviolet irradiation, which was far from the practical level.

Furthermore, in Patent Document 5, all polysilazane coating films are converted into silica by performing UV ozone oxidation under a large excess of oxygen supply for a long time (high-purity SiO having almost no Si—N bonds). ₂ thin film). When a gas barrier film is prepared by providing only the silica film thus formed on the resin base material, the internal stress remaining when the converted silica film shrinks and the characteristics of the inorganic (glass) film itself are very easy to break. It can be considered that the film has many defects. In this way, even if the thickness of the high-purity SiO ₂ thin film is simply increased or laminated to increase the thickness, it is not possible to suppress the occurrence of microcracks, nanocracks, etc. It can be said that it is difficult to obtain. One possible solution to the problem of cracking is to provide an intermediate layer such as a resin between the barrier layers. However, this is due to a cost increase due to a doubling of the coating process and poor adhesion to the inorganic barrier layer. At present, there are concerns about performance degradation or performance degradation due to gas permeation from the side of the intermediate layer, and it is difficult to achieve both cost reduction and high gas barrier properties.

  Therefore, high-speed film formation and high-speed processing are indispensable for producing a barrier film with roll-to-roll, low cost, high productivity and high gas barrier properties.

JP 2004-84027 A JP 2008-56967 A JP 2007-237588 A Japanese Patent Laid-Open No. 10-279362 JP 2008-159824 A

  An object of the present invention is to provide a highly stable gas barrier film that has a high gas barrier property and maintains a high gas barrier property even after bending, and a method for producing the gas barrier film that is highly productive and can be manufactured at low cost. It is to provide an organic electronic device having the gas barrier film.

  In the present invention, in addition to film formation by a coating method capable of roll-to-roll and high productivity, and an ultraviolet irradiation process capable of high-speed processing, a moisture trap region having a function of trapping invading moisture is provided. By combining with a gas barrier layer configuration having a specific structure sandwiched between two high-barrier regions, a gas barrier film having high gas barrier properties and stability could be provided at low cost with high productivity.

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

1. JIS K 7129B when forming from the support to the first high gas barrier region in the gas barrier film having the first high gas barrier region, the moisture trap region, and the second high gas barrier region in this order from the support side Water vapor permeability (water vapor permeability: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) (WVTR (g / m ² / day)) measured according to the method is 2 × 10 ⁻² to 1 × 10 ^A gas barrier film, wherein the second high gas barrier region contains a silicon compound and the moisture trap region contains a silicon compound containing a nitrogen atom derived from a silazane compound.

  2. 2. The gas barrier film as described in 1 above, wherein silicon dioxide is contained in the first high gas barrier region and the second high gas barrier region.

  3. In the moisture trap region, the atomic composition ratio of the silicon compound containing nitrogen atoms is Si: O: N = 1: 0.15 to 0.85: 0.15 to 0.85, 3. The gas barrier film according to 1 or 2.

4). In the method for producing a gas barrier film having the first high gas barrier region, the moisture trap region, and the second high gas barrier region in this order from the support side, when forming from the support to the first high gas barrier region Water vapor transmission rate (water vapor transmission rate: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) (WVTR (g / m ² / day)) measured according to the JIS K 7129B method is 2 × 10 ⁻² to A silicon compound containing a nitrogen atom derived from a silazane compound by applying a coating solution of a composition containing perhydropolysilazane on the first high gas barrier region which is 1 × 10 ⁻³ and then performing a conversion treatment. A method for producing a gas barrier film comprising forming a moisture trap region containing a second high gas barrier region containing a silicon compound in this order

  5. 5. The method for producing a gas barrier film as described in 4 above, wherein the conversion treatment is ultraviolet irradiation.

  6). An organic electronic device comprising the gas barrier film according to any one of 1 to 3 above.

  The present invention provides a highly stable gas barrier film that has a high gas barrier property and maintains a high gas barrier property even after bending, and a method for producing the gas barrier film that is highly productive and can be manufactured at low cost, and An organic electronic device having the gas barrier film could be provided.

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

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

<Gas barrier film>
First, the gas barrier film of the present invention will be described.

  The gas barrier film of the present invention is characterized by having a first high gas barrier region, a moisture trap region, and a second high barrier region in this order from the support side.

In the gas barrier film of the present invention, the water vapor permeability (water vapor permeability: 25 ± 0.5 ° C., relative humidity (90) of the film formed from the support to the first high gas barrier region was measured according to the JIS K 7129B method. ± 2)% RH) (WVTR (g / m ² / day)) is 2 × 10 ⁻² to 1 × 10 ⁻³ .

  In the present invention, the second high gas barrier region contains a silicon compound, and the moisture trap region contains a silicon compound containing a nitrogen atom derived from a silazane compound.

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

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

  Then, each element which comprises the gas barrier film of this invention is demonstrated.

<First high gas barrier region>
First, the first high gas barrier region in the present invention will be described.

In the first high gas barrier region in the present invention, the water vapor permeability (WVTR (g / m ² / day)) of the film formed from the support to the first high gas barrier region is 2 × 10 ⁻² to 1. If it will satisfy | fill gas barrier property of * 10 < ^-3 >, there will be no limitation in particular in a material and a layer structure.

  Specific materials applicable to the first high gas barrier region include inorganic oxides, inorganic nitrides, and inorganic oxynitrides. For example, metal oxides such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, indium tin oxide (ITO), metal nitrides such as silicon nitride and silicon oxynitride, metal oxynitrides Etc. Moreover, metals, such as aluminum, platinum, gold | metal | money, silver, nickel, chromium, can also be mentioned. As a method for forming the metal film on the plastic film, a vapor deposition method or a sputtering method as described later can be applied, but an aluminum foil or the like may be bonded to the plastic film.

  Among the materials described above, inorganic oxides, inorganic nitrides, or inorganic oxynitrides are preferable because of their high transparency. Of these, silicon compounds such as silicon oxide, silicon nitride, and silicon oxynitride are more preferable, and silicon dioxide is most preferable.

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

  The method for forming the first high gas barrier region is not particularly limited as long as the gas barrier property described above can be satisfied. However, the vacuum deposition method, the molecular beam epitaxial growth method, the ion cluster beam method, the low energy ion beam method, the ion Dry processes such as plating, CVD, sputtering, atmospheric pressure plasma, spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, etc. The application process can be selected, and can be appropriately selected depending on the material.

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

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

  When film formation is performed by a coating process, for example, a method of drying after applying a fine particle dispersion of an inorganic oxide or a sol-gel method of forming an inorganic oxide film from a precursor such as an alkoxide body can be applied. In addition, a method of obtaining a silicon oxide film by applying a conversion treatment to a coating film such as a silazane compound, a siloxane compound, an alkylsilane, or an alkoxysilane is more preferable because a higher gas barrier property can be easily formed in a short time. . More specifically, perhydropolysilazane, hexamethyldisilazane, silsesquioxane, hexamethyldisiloxane, tetramethylsilane, trimethylmethoxysilane, tetraethoxysilane and the like can be mentioned.

  Among these, it is most preferable to form from a composition containing perhydropolysilazane in that a denser silicon dioxide film can be obtained. The method for forming the silicon dioxide film from the composition containing perhydropolysilazane is the same as the method for forming the second high gas barrier region described later.

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

  The support in the present invention is not particularly limited as long as it can hold the first high gas barrier region in the present invention, but is applicable to mass production such as roll-to-roll and is easy to handle. A plastic film is preferable in that the cost can be reduced.

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

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

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

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

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

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

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

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

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

  Further, when the first high gas barrier region is formed on the support in the present invention, an anchor coating agent layer may be formed for the purpose of improving the adhesion of the layer to be formed to the support surface.

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

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

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

  In the present invention, between the support and the first high gas barrier region, a stress relaxation layer for relaxing stress applied to the gas barrier region, a smooth layer for smoothing the surface of the resin support, and a resin support It is preferable to provide a bleed-out preventing layer for preventing bleed-out from the body. Below, a stress relaxation layer, a smooth layer, and a bleed-out prevention layer are demonstrated.

(Stress relaxation layer)
In particular, when the first high gas barrier region is coated and formed on the resin support from the precursor compound, for example, when the silazane compound is converted into silicon oxide, the density is increased and the film shrinks. Concentration of may cause problems such as generation of cracks in the silicon oxide layer. In addition, there is a concern that cracks may occur due to bending stress received during handling or film conveyance.

  Therefore, for example, if a stress relaxation layer having physical properties such as hardness, density or elastic modulus located between the resin support and the silicon oxide layer is provided, it is considered that there is an effect of suppressing the occurrence of cracks. Yes.

  Specifically, the acrylic resin containing silica particles used for the smooth layer described later, the silazane compound or the siloxane compound used for forming the first and second high gas barrier regions of the present invention, and the like. It is possible to form a stress relaxation layer. For example, when designing the stress relaxation layer so that the density is lower than the upper high gas barrier region, even if the same material as the high gas barrier region is used, the progress of the conversion reaction is selected by the conversion method and conversion conditions, Alternatively, it can be controlled by appropriately selecting the thickness of the layer to be provided. It is also possible to control the obtained film density itself by selecting the material used for the stress relaxation layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 nm to 400 nm, preferably 200 nm 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, etc. are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

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

<Second high gas barrier region>
In the present invention, the second high gas barrier region contains a silicon compound.

  The silicon compound in the present invention is preferably an inorganic silicon compound, more preferably contains a silicon oxide compound, a silicon nitride compound, a silicon oxynitride compound, or a mixture thereof, and contains silicon dioxide. Is most preferred.

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

Moreover, it is thought that the 2nd high gas barrier property area | region in this invention should just have a gas-barrier property of at least 3 * 10 ^<-2> or less in a water-vapor-permeation rate.

  Since the second high gas barrier region in the present invention is formed together with the moisture trap region, it is difficult to directly measure the gas barrier property, but it is provided on a layer having no gas barrier property (below the detection limit). If the gas barrier property of the layer containing silicon dioxide substantially equivalent to that of the second high gas barrier region is obtained, it is considered that this is the gas barrier property of the second high gas barrier region.

Specifically, when Comparative Film 1-4B of Example 1 described later was treated under high temperature and high humidity, the layer having gas barrier properties was only a layer containing silicon dioxide (from Comparative Film 1-4A, silanol). It can be seen that the layer has no gas barrier property, but the silicon dioxide layer does not change at all even after treatment under high temperature and high humidity), and the gas barrier property is 3 × 10 ⁻² , so in the second high gas barrier region It can be said that the gas barrier property of the layer containing a certain silicon dioxide was confirmed to be 3 × 10 ⁻² .

Moreover, since the gas barrier property of the film which processed the comparative film 1-3A of Example 1 under high temperature and high humidity is 3 * 10 ^<-2 > like the comparative film 1-4B, as a 1st high gas barrier property area | region. It can be said that any applicable gas barrier region can be used as the second high gas barrier region.

  In other words, it is sufficient that the first and second high gas barrier regions have a gas barrier property that can prevent moisture permeation to such an extent that the moisture trap region described later does not lose its function. This is because the first and second high gas barrier regions sandwich the moisture trap region so that the function is maintained and the effect of the present invention can be obtained for the first time.

  However, the moisture trap region is a region that easily changes under normal circumstances because of its function, and thus it is difficult to form the moisture trap region independently.

  Therefore, in the present invention, the moisture trap region can be stably held by forming the second high gas barrier region together with the formation of the moisture trap region.

  Specifically, by forming a coating film using a silazane compound and then performing a conversion treatment, it is possible to simultaneously form a second high gas barrier region on the surface side and a moisture trap region therebelow. As the silazane compound, an inorganic polymer silazane compound such as perhydropolysilazane, a low-molecular silazane compound such as hexamethyldisilazane, or the like can be used. In the present invention, it is preferable to use a composition containing perhydropolysilazane in that a second high gas barrier region having high gas barrier properties can be formed.

  In the present invention, a plurality of second high gas barrier regions including a moisture trap region may be laminated on the second high gas barrier region, and the first high gas barrier region as described above may be stacked. A plurality of gas barrier regions may be stacked by using an applicable material, or a stress relaxation layer or the like may be stacked alternately with the gas barrier regions as described above.

  As a method for forming the second high gas barrier property region, the coating process mentioned above as the method for forming the first high gas barrier property region can be preferably used.

  When a film is formed using a silazane compound as a precursor, the second high gas barrier region and the moisture trap region can be finally formed by performing a conversion process. The conversion process will be described in detail later. To do.

<Composition containing perhydropolysilazane>
Then, the composition containing perhydropolysilazane in this invention is demonstrated.

  The composition containing perhydropolysilazane in the present invention is used when forming the moisture trap region and the second high gas barrier region. It is also useful for forming the first high gas barrier region of the present invention.

  The composition containing perhydropolysilazane in the present invention is not particularly limited as long as it contains perhydropolysilazane, and the material other than perhydropolysilazane in the composition can be applied with perhydropolysilazane and its solvent. Any material may be used as long as it has a certain level of compatibility.

  Further, the composition may contain a catalyst such as amine or metal added to promote the oxidation reaction at about 0.1 to 10% by mass relative to perhydropolysilazane. 5-5 mass% containing is preferable when reaction can be shortened.

  The content of perhydropolysilazane excluding the solvent and the catalyst in the composition is preferably 50% by mass or more, more preferably 80% by mass or more, and most preferably 100% by mass, that is, only composed of perhydropolysilazane. . If the content of perhydropolysilazane is 50% by mass or more, it is preferable in that a gas barrier property that can be applied to the high gas barrier property region is expected, and if it is 80% by mass or more, more preferable in terms of obtaining higher gas barrier properties When 100% by mass, a single layer coating film (in this case, the single layer does not mean that the composition is single, but refers to a film obtained by applying the coating liquid of the composition once) The treatment is more preferable in that the moisture trap region and the second high gas barrier region can be simultaneously formed on the first high gas barrier region.

  Examples of materials that can be obtained as perhydropolysilazane in the present invention include Aquamica NN120, NN110, NAX120, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

<Moisture trap area>
In the present invention, the moisture trap region is a layer containing a silicon compound containing a nitrogen atom derived from a silazane compound.

  As described above, the moisture trap region in the present invention is formed simultaneously with the second high gas barrier region from the silazane compound on the first high gas barrier region, so that the silicon compound containing a nitrogen atom derived from the silazane compound is formed. It can be formed as a layer containing.

  In the moisture trap region of the present invention, the atomic composition ratio of the layer containing the silicon compound containing nitrogen atoms is Si: O: N = 1: 0.15 to 0.85: 0.15 to 0.85. It is preferable that Si: O: N = 1: 0.15 to 0.35: 0.65 to 0.85, and Si: O: N = 1: 0.25 to 0.35: More preferably, it is 0.65-0.75.

The atomic composition ratio in the thin film can be confirmed by combining sputtering and XPS surface analysis. By performing the etching from the film surface in the depth direction by sputtering, the composition ratio of each atom (Si, O, N, C, etc.) detected using the XPS surface analyzer is obtained. The atomic composition ratio in each of the gas barrier region, the moisture trap region, and the second high gas barrier region can be confirmed. However, the atomic composition ratio obtained by this method represents a ratio in which each atom is present in the film, and the ratio does not always form a single compound, A case of a mixture of compounds (for example, SiO ₂ + SiO _x N _y or SiO ₂ + Si _x N _y ) is also included.

  Further, it is considered that the moisture trapping ability of the moisture trapping region in the present invention can be measured by obtaining an increase ΔSiOH of the amount of silanol generated by the reaction with moisture.

  This ΔSiOH can be obtained by using time-of-flight secondary ion mass spectrometry (Tof-SIMS) in the film depth direction.

When the relative Si ion intensity detected by Tof-SIMS is normalized to 1, the water trapping capacity of the water trapping region in the present invention is
ΔSiOH = (relative SiOH ionic strength of moisture trap region after 90 ° C. treatment at 60 ° C.) − (Relative SiOH ionic strength of moisture trap region immediately after fabrication) −
Can be obtained as

  In the present invention, the moisture trapping capacity ΔSiOH (60 ° C. 90% 3 day treatment) of the moisture trapping region is preferably about 0.01 to 0.2, more preferably about 0.05 to 0.1. preferable.

  Here, the time-of-flight secondary ion mass spectrometry will be described.

(Time-of-flight secondary ion mass spectrometry: Tof-SIMS)
Time-of-flight secondary ion mass spectrometry is commonly referred to as Tof-SIMS (Time-Of-Flight Secondary Ion Spectrometry). In principle, the sample is irradiated with pulsed ions in a high vacuum, and the ions removed from the surface by the sputtering phenomenon are detected by dividing them by weight (atomic weight, molecular weight). Then, the chemical species (atoms, molecules) existing on the outermost surface of the sample can be estimated from the pattern (mass spectrum) of the weight and the detected amount.

  More specifically, the analysis is performed through the following two stages.

  (1) Secondary ion emission: Various particles are released from the sample surface by sputtering phenomenon from the sample surface irradiated with ions (primary ions) in a pulsed manner on the solid sample surface and subjected to ion bombardment.

  In particular, in Tof-SIMS, the current density of primary ions is kept low (static mode), and sputtering is performed without destroying the sample surface as much as possible.

  (2) Mass separation and detection: Take out ions (secondary ions) present in the particles released by sputtering, and divide and detect them by their weight (mass) to analyze the composition from the sample surface to the inside. The method is secondary ion mass spectrometry.

  Tof-SIMS employs a time-of-flight analyzer for mass separation. The ions that are drawn into the flight tube by the electric field fly faster in the lighter and slower in the flight tube and reach the detector.

  This flight time is converted into mass and mass separation is performed. By using the time-of-flight type, high sensitivity, high mass resolution, and detection of high mass materials are possible.

  As a result, not only the two-dimensional distribution of chemical species existing on the surface can be known, but also the element composition analysis in the depth direction in a shallow region can be performed by repeatedly cutting and measuring the surface with an ion beam. Moreover, the relative abundance of the detected chemical species can also be determined.

  In the present invention, even a layer composed of a single compound or a layer forming a uniform region as a mixture is recognized as a single region if a clear interface can be confirmed. . In the present invention, the presence of a clear interface in each region can be clearly confirmed by a TEM cross-sectional photograph.

  Moreover, since it can be said that this moisture trap layer exists as an intermediate layer between two high gas barrier regions, it is considered that there is also an effect of preventing cracks that are likely to occur when only the barrier layer is thickened. . Thereby, since bending resistance can be improved, maintaining high gas barrier property, high stability is securable.

Moreover, in the resin intermediate layer generally used, problems such as film peeling are likely to occur due to poor adhesion with an inorganic film such as SiO ₂ , which may lead to performance deterioration.

  On the other hand, since the moisture trap region in the present invention is an inorganic film derived from the same raw material as the high gas barrier property region, the adhesion is good and the performance stability can be further improved.

  In order to simultaneously form the moisture trap region and the second high gas barrier region from one coating film as in the present invention, a conversion treatment described later may be performed on the coating film of the silazane compound under appropriate conditions. That is, the coating film thickness and the conversion treatment condition may be optimally combined. By optimizing the conversion treatment conditions according to the film thickness, a layer containing silicon dioxide (second high gas barrier region) is formed on the surface layer portion of the coating film, and below the layer containing silicon dioxide A layer (moisture trap region) containing a silicon compound containing a nitrogen atom derived from a silazane compound is formed.

  The following mechanism is considered as the reason why two or more layers having different compositions can be easily formed by the conversion treatment of the single-layer coating film. That is, since the conversion reaction from polysilazane to silicon dioxide proceeds from the surface layer portion of the coating film, once a layer containing high-density silicon dioxide is formed on the surface layer portion, the reactive oxygen species necessary for the oxidation treatment Cannot penetrate in the depth direction of the film thickness. Thus, it is considered that a layer containing a silicon compound having a high nitrogen atom content is formed in the lower layer of the silicon dioxide layer by inhibiting the formation of the silicon dioxide layer by the oxidation reaction.

  Specifically, when the supply of oxygen is insufficient, for example, when irradiated with energy rays such as ultraviolet rays, the polysilazane undergoes a structural change to a silicon oxynitride compound and can be present to some extent in the film. Become. The silicon oxynitride compound formed in this way can be said to be an intermediate that can further change the structure. However, since the silicon oxynitride compound is sandwiched between two layers containing silicon dioxide having high gas barrier properties, the structure is maintained. I think you can.

  Further, the point that the first high gas barrier region is essential on the support in obtaining the specific configuration of the present invention can be explained as follows.

  That is, when a polysilazane coating film is formed on a support without gas barrier properties (having moisture permeation from below) and subjected to a conversion treatment, a layer containing silanol-rich silicon dioxide on the support immediately after the formation, On top of that, a layer containing a silicon compound having a high nitrogen atom content, a layer containing crystal-like high-density silicon dioxide on the surface layer, and three types of layers were once formed (Comparative film 1 of Example 1 -3A), a silicon compound layer with a high nitrogen atom content (that is, a moisture trap region) that is not blocked on the lower side by a gas barrier layer (that is, a first high gas barrier region) is a lower side (support side) Silanolization proceeds due to moisture intruding from the layer, and eventually the layer changes to a layer containing silanol-rich silicon dioxide.

  Therefore, in order to stably obtain the moisture trap region and the second gas barrier region thereon, it is essential to form the moisture trap region on the first gas barrier region. This is because, in the gas barrier film 1-4B of Example 1 that does not have the first gas barrier region, the moisture trap region cannot be stably present (all converted to a silanol-rich silicon dioxide layer after high temperature and high humidity treatment). It is clear from that).

  As described above, the moisture trap region containing the nitrogen atom of the present invention that is reactive with moisture cannot exist stably in a normal environment. It has been found that when it is used as one of the constituent elements of a gas barrier film by exhibiting a trap function, it is effective to obtain higher gas barrier properties.

<Conversion processing>
In the present invention, after applying a coating solution of a composition containing a silazane compound on the first high gas barrier region, a conversion treatment (also referred to as an oxidation treatment or a modification treatment) is performed, so that the moisture trap region and The second high gas barrier region can be efficiently formed simultaneously in this order.

  The conversion treatment referred to in the present invention is an oxidation treatment of a silazane compound by a method described later.

  By performing the conversion treatment, as described above, the second high gas barrier property region containing hard and dense silicon dioxide can be formed on the surface, and the silicon atom containing nitrogen atoms having reactivity under the second high gas barrier property region can be formed. A moisture trap region containing a compound can be stably present.

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

  Any appropriate method can be adopted as a coating method of the coating liquid of the composition containing the silazane compound. 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 film thickness of the second high gas barrier region including the moisture trap region formed from the composition containing the silazane compound provided on the first gas barrier region is preferably in the range of 30 to 2000 nm, more preferably 40 to 40 nm. It is the range of 500 nm, Most preferably, it is the range of 40-300 nm.

  One set of the second high gas barrier region including the moisture trap region formed from the composition containing the silazane compound is sufficiently effective, but a plurality of similar layers may be stacked. Furthermore, as a protective layer of the gas barrier film, one or more organic polysiloxanes or organic resin layers as mentioned above in the stress relaxation layer may be provided thereon.

  The coating film (coating film) formed by applying the coating liquid of the composition containing the silazane compound is subjected to a conversion treatment, and the silazane compound contained in the composition is converted into silicon dioxide or silicon oxynitride.

  As a method of forming a region containing a silicon compound containing a nitrogen atom as a moisture trap region and a region containing silicon dioxide as a second high gas barrier region on the first high gas barrier region, If a coating film having a film thickness (the optimum value varies depending on the presence or absence of a catalyst, for example, 50 nm or more) is provided, a low-temperature heat treatment (hot plate, oven, electric furnace, flash lamp annealing apparatus, etc.) of about 80 to 200 ° C. ) Or plasma irradiation treatment in an oxidizing gas atmosphere or the like, it is possible to obtain the desired configuration. However, if you select a conversion method that can form a denser silicon dioxide layer, you can not only widen the range of film thickness selection by adjusting the processing conditions, but also ensure an unstable moisture trap region in the atmosphere. Furthermore, it is preferable because it can be confined between the first high gas barrier region and the second high gas barrier region.

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

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

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

  The conversion treatment applied to the composition containing the silazane compound is preferably a light irradiation treatment in that a denser film can be formed in a short time.

  Furthermore, the light irradiation treatment is more preferably performed in combination with the heat treatment.

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

  Since this active oxygen and ozone are very reactive, the polysilazane in the coating film formed from the composition containing the silazane compound is oxidized directly without passing through silanol, resulting in higher density and defect. Less silicon dioxide film 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 to 450 nm, and more preferably vacuum ultraviolet light of about 150 to 300 nm is irradiated.

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

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

  By irradiating the polysilazane in the coating film formed from the composition containing perhydropolysilazane with ultraviolet rays, the polysilazane is converted into a high-density silicon oxide film, that is, a high-density silica film. The film thickness and density of the silica film can be controlled by the intensity of ultraviolet light, irradiation time, and wavelength (light energy density), and can be appropriately selected, such as using different types of lamps to obtain a desired film structure. Is possible. In addition to continuous irradiation, multiple irradiations may be performed, and the multiple irradiations 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 the reaction (also referred to as oxidation reaction, conversion treatment, or modification treatment). The heating method is such that the substrate is brought into contact with a heating element such as a heat block, the coating film is heated by heat conduction, the atmosphere is heated by an external heater such as a resistance wire, and infrared light such as an IR heater is applied. Although the method used etc. are mentioned, it does not specifically limit. You may select suitably the method which can maintain the smoothness of a coating film.

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

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

  In the present invention, it is preferable that the coating solution of the composition containing perhydropolysilazane is applied to the first high gas barrier region, dried, and then converted by a method of irradiating with vacuum ultraviolet rays. This vacuum ultraviolet irradiation breaks the molecular bond of polysilazane, and even a small amount of oxygen in the film or atmosphere can be efficiently converted into ozone or active oxygen. Silica modification) is promoted, and the resulting ceramic film becomes denser. VUV light irradiation is effective at any time point after the coating film is formed.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time. Therefore, compared to low-pressure mercury lamps with 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. .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it is smaller than this, the effect of diffraction is generated and colored.

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

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

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

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

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

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

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

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

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

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

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

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

Example 1
First, comparative films 1-1A to 1-3A and gas barrier films 1-1B to 1-3B of the present invention were produced.

<Production of Comparative Films 1-1A to 1-3A and Gas Barrier Films 1-1B to 1-3B of the Present Invention>
(Support)
In the present invention, as a support (FIGS. 4 and 5), a 125 μm thick polyester film (Tetron O3, manufactured by Teijin DuPont Film Co., Ltd.) having both surfaces subjected to easy adhesion processing is annealed at 170 ° C. for 30 minutes. After that, the following bleed-out prevention layer (not shown in FIG. 4) prepared on the back side was used.

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

<Comparative film 1-1A>
As the support 5, a polyester film having a thickness of 125 μm in which the bleed-out prevention layer was formed on the back surface side was used. On this support, a silicon dioxide film was formed to a thickness of about 100 nm by sputtering to obtain a comparative film 1-1A having a high barrier region (FIGS. 4 and 3).

<Gas barrier film 1-1B of the present invention>
On the comparative film 1-1A obtained above, a 20% by mass dibutyl ether solution of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NAX120-20, amine catalyst type) and a 20% by mass dibutyl ether of perhydropolysilazane. A solution (manufactured by AZ Electronic Materials Co., Ltd., Aquamica NN120-20, non-catalytic type) was mixed at a mass ratio of 1: 4, and then a solution diluted to 4% by mass with dibutyl ether was used for spin coating. After coating at (5000 rpm, 60 seconds), it was dried at 80 ° C. for 1 minute to form a perhydropolysilazane coating film.

  Furthermore, using a stage movable type xenon excimer irradiation device (MD excimer, MECL-M-1-200), excimer lamp irradiation (distance between excimer light source lamp and substrate: 3 mm, stage temperature: 100 ° C., Oxygen concentration in the processing environment: 0.1%, transported 10 times at a stage moving speed of 10 mm / sec.) To the second high gas barrier region 1 in which the surface of the membrane is made of silicon dioxide, A gas barrier film 1-1B (FIG. 4, 4: None) of the present invention in which 40 nm was converted into a moisture trap region 2 made of a silicon compound containing a nitrogen atom was produced.

  Here, the film thickness of each area | region was confirmed by the clear interface being seen from the cross-sectional photograph of TEM (Transmission Electron Microscope: Transmission electron microscope).

  The composition of each region was confirmed by a combination of sputtering and XPS surface analysis.

  Etching from the surface to the depth direction using the sputtering method, and using the XPS surface analyzer, the outermost surface was set to 0 nm, sputtering was performed at a rate of 0.5 nm / min, and the atomic composition ratio was measured. Up to about 10 nm, the ratio of Si: O is approximately 1: 2 (second high gas barrier region, FIGS. 4 and 1), and from there to the first high gas barrier region (silicon dioxide layer). Up to about 40 nm, the Si: O: N ratio is almost uniformly 1: 0.35: 0.65 (moisture trap region, FIGS. 4 and 2), and further supported from the first high gas barrier region below it. It was found that 100 nm up to the body was a silicon dioxide layer.

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

<Comparative film 1-2A>
As the support 5, a polyester film having a thickness of 125 μm in which the bleed-out preventing layer was formed on the back side and the following smooth layer was formed on the front side was used. On this support, a silicon dioxide film is deposited by plasma CVD (using oxygen gas and tetraethoxysilane as the source gas, and adjusting the source gas supply rate and energy output density to increase the deposition rate. Comparative film 1-2A having a high gas barrier property region (FIGS. 4 and 3) was obtained.

(Production of smooth layer)
On the surface side of the support (FIGS. 4 and 5), a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied, and after applying with a wire bar so that the film thickness after drying was 4 μm, Drying conditions: after drying at 80 ° C. for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, curing conditions: curing at 1.0 J / cm ² to produce a smooth layer (clear hard coat layer: CHC layer) ( (Omitted in FIG. 4).

<Gas barrier film 1-2B of the present invention>
In the same manner as the gas barrier film 1-1B, the moisture trap region (FIGS. 4 and 2) and the second high gas barrier were formed on the comparative film 1-2A having the first high gas barrier region in the present invention obtained above. The gas barrier film 1-2B of the present invention provided with the property region (FIGS. 4, 1) was obtained (FIG. 4, 4: None).
Similarly to the gas barrier film 1-1B, from the cross-sectional photograph of TEM and the XPS surface analysis, about 10 nm from the film surface is the second high gas barrier region 1 (silicon dioxide layer), and about 40 nm below it is It was found that the moisture trap region 2 (Si: O: N = 1: 0.25: 0.7), and further about 100 nm below it was the first high gas barrier region (silicon dioxide layer).

<Comparative film 1-3A>
As a support (FIGS. 4 and 5), a 125 μm-thick polyester film in which the bleed-out prevention layer was formed on the back side and the following smooth layer was formed on the front side was used. On this support, in the same manner as the production of the gas barrier film 1-1B of the present invention, a perhydropolysilazane coating film is formed and then subjected to a conversion treatment, so that about 10 nm from the surface of the film is made of silicon dioxide. Comparative film 1 in which a high gas barrier region (FIGS. 4 and 3) is converted into a silicon compound layer containing about 20 nm below it and a silicon compound layer containing about 20 nm below it into a silanol-rich silicon dioxide layer. -3A was produced.

  Here, the silanol-rich silicon dioxide layer represents a silica layer containing a large amount of SiOH (silanol) in which a part of Si atoms are substituted with OH groups. In the silanol-rich silicon dioxide layer, the ratio of Si: O is almost uniformly 1: 2.2, and the presence of silanol groups is Tof-SIMS (Time-Of-Flight Secondary Ion Spectrometry: time of flight). Type secondary ion mass spectrometry).

  By the way, after the comparative film 1-3A was treated under wet thermo (60 ° C., 90% RH) for 3 days, the composition of each region was confirmed in the same manner as described above. Although there was no change in the first high gas barrier region (FIGS. 4 and 3), the silicon compound layer containing nitrogen atoms that was about 20 nm below it disappeared, and further, the silanol-rich layer that was about 20 nm below it disappeared. The film thickness of the silicon dioxide layer was 40 nm. From this, it was confirmed that the silicon compound layer containing nitrogen atoms not sandwiched between the high gas barrier regions was all changed to a silanol-rich silicon dioxide layer under high temperature and high humidity.

<Gas barrier film 1-3B of the present invention>
In the same manner as the gas barrier film 1-1B, the moisture trap region 2 and the second high gas barrier region 1 are provided on the comparative film 1-3A having the first high gas barrier region in the present invention obtained above. Moreover, the gas barrier film 1-3B of the present invention was obtained (FIGS. 4 and 4: Silanol-rich silicon dioxide layer / silicon compound layer containing nitrogen atoms).

  Further, similarly to the gas barrier film 1-1B, from the cross-sectional photograph of TEM and the XPS surface analysis, about 10 nm from the film surface is the second high gas barrier region (FIGS. 4, 1) (silicon dioxide layer), It was found that approximately 40 nm below is a moisture trap region (FIGS. 4 and 2) (Si: O: N = 1: 0.25: 0.75).

<Comparative film 1-4A>
As the support 5, a polyester film having a thickness of 125 μm in which the bleed-out preventing layer was formed on the back side and the following smooth layer was formed on the front side was used. On this support, the perhydropolysilazane coating film was formed in the same manner as in the production of the gas barrier film 1-1B of the present invention, and was not subjected to a conversion treatment by excimer lamp irradiation, but a wet thermo (60 ° C., 90% RH). The comparative film 1 in which all regions on the support were converted to a silanol-rich silicon dioxide layer (approximately 70 nm) by heating at 100 ° C. for 5 minutes on a hot plate after being treated for 5 minutes under -4A was produced.

<Comparative film 1-4B>
On the comparative film 1-4A obtained above, in the same manner as the production of the gas barrier film 1-1B, after forming a perhydropolysilazane coating film, by applying a conversion treatment by excimer lamp irradiation, the surface of the film is approximately 10 nm is a silicon dioxide layer, 20 nm below that is a silicon compound layer containing nitrogen atoms (Si: O: N = 1: 0.85: 0.55), and about 90 nm from the bottom to the support is silanol. Comparative film 1-4B having a rich silicon dioxide layer was produced.

  By the way, after the comparative film 1-4B was treated under wet thermo (60 ° C., 90% RH) for 3 days, the composition of each region was confirmed in the same manner as described above. Although there was no change in the second high gas barrier region 3, the silicon compound layer containing nitrogen atoms that was approximately 20 nm below it disappeared, and further a film of a silanol-rich silicon dioxide layer that was approximately 90 nm below it. The thickness was 110 nm. From this, it was confirmed that the silicon compound layer containing nitrogen atoms not sandwiched between the high gas barrier regions was all changed to a silanol-rich silicon dioxide layer under high temperature and high humidity.

<Comparative film 1-5A>
As the support 5, a polyester film having a thickness of 125 μm in which the bleed-out preventing layer was formed on the back side and the following smooth layer was formed on the front side was used. On this support, in the same manner as the comparative film 1-2A, the plasma CVD method (with introduction of oxygen gas, tetraethoxysilane was used as the source gas, and the source gas supply amount and the energy output density were adjusted. Comparative film 1-5A was obtained by forming a silicon dioxide film with a thickness of about 50 nm by adjusting the speed so as to be extremely low.

<Comparative film 1-5B>
On the comparative film 1-5A obtained above, in the same manner as the gas barrier film 1-1B of the present invention, a silicon compound having a silicon dioxide layer of about 10 nm from the surface of the film and a nitrogen compound of about 40 nm below it is a nitrogen atom. Comparative film 1-5B having a layer (Si: O: N = 1: 0.25: 0.75) was produced.

<Reference Example Film 1-6>
A polyester film having a thickness of 125 μm and having a bleed-out preventing layer on the back side and a smooth layer on the front side used for the production of the gas barrier film was used as Reference Example Film 1-6.

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

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

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

(apparatus)
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Laser microscope: KEYENCE VK-8500
Atomic force microscope (AFM): DI3100 manufactured by Digital Instruments
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Production of evaluation cell)
I want to vapor-deposit a gas barrier member sample before applying a transparent conductive film on a gas barrier layer surface (also referred to as a ceramic layer surface) of a gas barrier member (gas barrier film) using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.) Masking was performed except for portions (9 locations of 12 mm × 12 mm), 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.

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

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

Comparative films 1-1A to 1-5A, 1-4B to 1-5B, 1-6, and water vapor permeability (WVTR (g / m) measured for the gas barrier films 1-1B to 1-3B of the present invention, respectively. ² / day)) are summarized in Table 1.

  From the results of Table 1, the gas barrier films 1-1B to 1-3B of the present invention all have high gas barrier properties, and after the wet thermo treatment (60 ° C., 90% RH) treatment and after the bending treatment, water vapor is also obtained. It was found that there was no deterioration in transmittance.

  On the other hand, it was found that the comparative films 1-1A to 1-4A and 1-4B all had only a low gas barrier property.

Furthermore, on the comparative film 1-5A showing a very high gas barrier property of 9 × 10 ⁻⁴ or less before the WVTR of the support to the first high gas barrier region is deteriorated (wet thermo treatment or bending treatment) Furthermore, as in the present invention, the comparative film 1-5B provided with the moisture trap region and the second high gas barrier property region shows a high gas barrier property before the bending treatment, but there is an extreme decrease in gas barrier property after the bending treatment. I can see that.

  In Comparative Film 1-5A, although the initial gas barrier property is high, it is very easy to break, and when a defect is formed even at one point, stress concentrates on that point, and thus the barrier film suddenly breaks down. This is thought to be due to this. Therefore, bending resistance is also low and stability cannot be ensured.

As described above, in the gas barrier film of the present invention, since the first high barrier region having a relatively low gas barrier property such as WVTR of 1 × 10 ⁻² to 1 × 10 ⁻³ is used, the gas barrier film is rapidly broken. Since it hardly occurs and the bending resistance is high, the stability of the gas barrier film can be remarkably improved.

Example 2
Using the gas barrier film prepared in Example 1, a gas barrier film having the following transparent conductive film was prepared. Subsequently, the organic photoelectric conversion element was produced using the gas barrier film which has a transparent conductive film. As the gas barrier film, comparative films 1-1A to 1-3A, 1-5A, 1-4B, 1-5B, and the gas barrier films 1-1B to 1-3B of the present invention were used, respectively, and organic photoelectric conversion elements. 2-1A to 2-3A, 2-5A, 2-4B, and 2-5B were prepared.

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

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

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

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

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

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

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

  On the surface of the obtained transparent substrate, Baytron P4083 (made by Starck Vitec), which is a conductive polymer, is applied and dried so as to have a film thickness of 30 nm, followed by heat treatment at 150 ° C. for 30 minutes, and a hole transport layer. Was formed.

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

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

Next, the transparent substrate on which the series of functional layers 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 the deposition rate is 0.01 nm / second. Laminate 0.6 nm of lithium fluoride, and then continue through a shadow mask with a width of 2 mm (deposit the light receiving part so as to be 2 × 2 mm), and deposit 100 nm of Al metal at a deposition rate of 0.2 nm / sec. Thus, a second electrode was formed.

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

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

  Thus, an organic photoelectric conversion element sealed on both sides was obtained.

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

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

A: 70% or more B: 40% or more, less than 70% Δ: 20% or more, less than 40% ×: less than 20% Table 2 shows the evaluation results.

  From Table 2, it was found that the durability of the organic photoelectric conversion device of the present invention was remarkably superior to that of the comparative organic photoelectric conversion device.

DESCRIPTION OF SYMBOLS 1 2nd high gas-barrier area | region 2 Moisture trap area | region 3 1st high gas-barrier area | region 4 Between a support body and 1st high gas-barrier area | region 5 Support body 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Anode 13 Cathode 14 Power generation layer (bulk heterojunction layer)
14p p layer 14i i layer 14n n layer 14 'first power generation layer 15 charge recombination layer 16 second power generation layer 17 hole transport layer 18 electron transport layer

Claims (6)

JIS K 7129B when forming from the support to the first high gas barrier region in the gas barrier film having the first high gas barrier region, the moisture trap region, and the second high gas barrier region in this order from the support side Water vapor permeability (water vapor permeability: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) (WVTR (g / m ² / day)) measured according to the method is 2 × 10 ⁻² to 1 × 10 ^A gas barrier film, wherein the second high gas barrier region contains a silicon compound and the moisture trap region contains a silicon compound containing a nitrogen atom derived from a silazane compound.   The gas barrier film according to claim 1, wherein silicon dioxide is contained in the first high gas barrier region and the second high gas barrier region.   In the moisture trap region, an atomic composition ratio of a silicon compound containing a nitrogen atom is Si: O: N = 1: 0.15 to 0.85: 0.15 to 0.85. Item 3. The gas barrier film according to Item 1 or 2. In the method for producing a gas barrier film having the first high gas barrier region, the moisture trap region, and the second high gas barrier region in this order from the support side, when forming from the support to the first high gas barrier region Water vapor transmission rate (water vapor transmission rate: 25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) (WVTR (g / m ² / day)) measured according to the JIS K 7129B method is 2 × 10 ⁻² to A silicon compound containing a nitrogen atom derived from a silazane compound by applying a coating solution of a composition containing perhydropolysilazane on the first high gas barrier region which is 1 × 10 ⁻³ and then performing a conversion treatment. A method for producing a gas barrier film comprising forming a moisture trap region containing a second high gas barrier region containing a silicon compound in this order   The method for producing a gas barrier film according to claim 4, wherein the conversion treatment is ultraviolet irradiation.   An organic electronic device comprising the gas barrier film according to claim 1.

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