JPWO2016140340A1 - Optical film and optical device using the same - Google Patents

Abstract

In an optical film in which a light emitting layer containing quantum dots (QD) is sandwiched between two gas barrier films having an inorganic barrier layer made of an inorganic compound disposed on a substrate, the inorganic barrier layer and the light emitting layer (Particularly under high-temperature and high-humidity conditions) and a means capable of suppressing the deterioration of the gas barrier properties over time. A light emitting layer containing semiconductor nanoparticles and an ultraviolet curable resin, a base material, an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material, and the base material of the inorganic barrier layer An optical film having an adhesive layer disposed on a surface opposite to the surface, and a pair of gas barrier films sandwiching the light emitting layer so that the adhesive layer is in contact with the light emitting layer. The film thickness (measured with a transmission electron microscope) was 30 nm or less, and the peel strength between the inorganic barrier layer and the light-emitting layer (measured with a peel tester FGPX-0.5 manufactured by SHIMPO) was 2 N / 20 mm or more. [Selection] Figure 1

Description

  The present invention relates to an optical film and an optical device using the same.

  In recent years, semiconductor nanoparticles (also referred to as “Quantum Dot (QD)”) have attracted commercial attention because their electronic properties can be adjusted by their size. Semiconductor nanoparticles are used in a wide variety of fields, such as biolabeling, solar power generation, catalysis, bioimaging, light emitting diodes (LEDs), general spatial lighting, and electroluminescent displays. Is expected.

  Here, it is known that semiconductor nanoparticles deteriorate when they come into contact with water vapor or oxygen, and various methods for blocking the semiconductor nanoparticles from water vapor or oxygen have been proposed.

  For example, in Japanese translations of PCT publication No. 2013-544018 and International Publication No. 2014/113562, a quantum dot layer (light emitting layer) in which phosphor particles functioning as quantum dots (QD) are dispersed in an ultraviolet curable resin or a thermosetting resin. It is disclosed to dispose a gas barrier film so as to sandwich the film.

  In JP-A-10-156998, an inorganic oxide thin film is provided on one surface of a flexible plastic substrate, and a silane coupling agent thin film is further formed on the inorganic oxide thin film. A technique for forming a transparent barrier film by providing a film is disclosed. Here, as a silane coupling agent, what was organized by a vinyl group, a methacryloxy group (methacryloyl group), an amino group, an epoxy group, a mercapto group, etc. is disclosed. In the technique disclosed in Japanese Patent Laid-Open No. 10-156998, by providing a thin film made of a silane coupling agent, the adhesion between the inorganic oxide thin film (inorganic barrier layer) and the heat-meltable heat-sealable resin is improved. We are trying to improve.

  The present inventor makes an optical film in which a light emitting layer containing quantum dots (QD) is sandwiched between two gas barrier films having an inorganic barrier layer made of an inorganic compound disposed on a substrate. Various studies have been conducted on techniques for suppressing the penetration of water vapor and oxygen into the light emitting layer and preventing the deterioration of the semiconductor nanoparticles contained in the light emitting layer. As a result, when the inorganic barrier layer of a gas barrier film using a conventionally known inorganic barrier layer is arranged as it is adjacent to the light emitting layer containing semiconductor nanoparticles, a general adhesive layer (film thickness) It has been found that the adhesion between the inorganic barrier layer and the light emitting layer decreases with time when these are adhered via 100 nm to). It has also been found that such a problem of lowering adhesiveness is particularly prominent when the laminate is placed under conditions of high temperature and high humidity. Here, if the adhesion between the inorganic barrier layer constituting the gas barrier film and the light emitting layer is not sufficient, the effect of blocking the oxygen and moisture by the inorganic barrier layer with respect to the light emitting layer is reduced, and as a result, light emission from the light emitting layer. There is also a risk that the luminance is lowered.

  The present invention has been made in view of the above circumstances, and a light emitting layer containing quantum dots (QD) is sandwiched between two gas barrier films having an inorganic barrier layer made of an inorganic compound disposed on a substrate. It is an object of the present invention to provide a means capable of suppressing the deterioration of the adhesion and gas barrier properties of the inorganic barrier layer and the light emitting layer (especially under high temperature and high humidity conditions) over time.

  The present inventor has intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by controlling the thickness of the adhesive layer provided between the inorganic barrier layer and the light emitting layer and the peel strength between these layers to predetermined values. It came to complete.

  That is, according to one aspect of the present invention, a light emitting layer containing semiconductor nanoparticles and an ultraviolet curable resin, a base material, an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material, and the above An optical film having an adhesive layer disposed on the surface of the inorganic barrier layer opposite to the substrate and having a pair of gas barrier films sandwiching the light emitting layer so that the adhesive layer is in contact with the light emitting layer Is provided. In the optical film, the thickness of the adhesive layer (measured by a transmission electron microscope) is 30 nm or less, and the peel strength between the inorganic barrier layer and the light emitting layer (manufactured by SHIMPO) It is characterized in that (measured with a peeling tester FGPX-0.5) is 2 N / 20 mm or more.

It is a schematic sectional drawing which shows one Embodiment of the laminated constitution of the optical film which concerns on this invention. It is a schematic sectional drawing which shows one Embodiment of the laminated constitution of the gas barrier film which concerns on this invention.

  According to one embodiment of the present invention, a light emitting layer containing semiconductor nanoparticles and an ultraviolet curable resin, a base material, an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material, and the inorganic barrier Provided is an optical film having an adhesive layer disposed on the surface of the layer opposite to the base material and a pair of gas barrier films sandwiching the light emitting layer so that the adhesive layer is in contact with the light emitting layer Is done. In the optical film, the thickness of the adhesive layer (transmission electron microscope (measured by TEM) is 30 nm or less, and the peel strength between the inorganic barrier layer and the light emitting layer (SHIMPO) It is characterized in that it is 2N / 20 mm or more (measured with a peel tester FGPX-0.5 manufactured by company).

  As described above, according to the optical film of the present invention, it is possible to suppress the deterioration of the adhesion and gas barrier properties over time between the inorganic barrier layer and the light emitting layer (particularly under high temperature and high humidity conditions), Ultimately, it is possible to prevent the luminance of the light emitting layer from decreasing with time. Here, although the mechanism by which the above-described effects of the configuration of the present invention are exerted is not completely clear, the interface between the inorganic barrier layer and the light emitting layer is firmly bonded, and as a result, adhesion is improved. Therefore, it is estimated that the deterioration of the gas barrier property with time and the deterioration of the semiconductor nanoparticles accompanying this are suppressed. In addition, as a result of the adhesive layer being made very thin, oxygen and moisture intrusion from the side surface of the adhesive layer can be suppressed, which also leads to suppression of gas barrier degradation and semiconductor nanoparticle degradation. It is thought that there is. In addition, this invention shall not be limitedly interpreted by the said mechanism in any way.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios. In this specification, “X to Y” indicating a range means “X or more and Y or less”. Furthermore, unless otherwise specified, measurements such as operation and physical properties are performed under conditions of room temperature (25 ° C.) / Relative humidity 40 to 50% RH.

≪Optical film≫
The optical film according to the present invention has a light emitting layer and a pair of gas barrier films that sandwich the light emitting layer. Here, the layer structure of the optical film according to one embodiment of the present invention will be described with reference to FIG.

  In FIG. 1, an optical film 1 according to an embodiment of the present invention has a configuration in which a light emitting layer 20 is sandwiched between a pair of gas barrier films 11. Here, the gas barrier film 11 has a configuration in which a base material 12, an inorganic barrier layer 13, and an adhesive layer 14 are laminated in this order. The gas barrier film 11 sandwiches the light emitting layer 20 in a state where the inorganic barrier layer 13 constituting the film is disposed on the light emitting layer 20 side with respect to the base material 12.

  Hereinafter, the constituent elements of the optical film according to the present invention will be described in the order of the gas barrier film and the light emitting layer.

<Gas barrier film>
As shown in FIG. 1, the gas barrier film has a configuration in which a substrate 12, an inorganic barrier layer 13, and an adhesive layer 14 are laminated in this order.

[Base material]
The substrate of the gas barrier film according to the present invention is not particularly limited as long as the inorganic barrier layer can be retained. As the substrate, a resin substrate (plastic film or sheet) is usually used, and a film or sheet (resin substrate) made of a colorless and transparent resin is preferably used as the substrate. The resin substrate used is not particularly limited in material, thickness, etc. as long as it is a film that can hold an inorganic barrier layer or a layer (hard coat layer, quantum dot layer, etc.) provided on the inorganic barrier layer in the future. It can be appropriately selected according to the purpose of use.

  For example, poly (meth) acrylic 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, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resin films, organic-inorganic hybrid structures Heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having a basic skeleton as well as a resin film formed by laminating two or more layers of the above resin. Rukoto can.

  The thickness of the substrate is not particularly limited, but is preferably 5 to 300 μm, and more preferably 10 to 100 μm. The substrate may have a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer. As the functional layer, in addition to those described above, those described in paragraph numbers “0036” to “0038” of JP-A-2006-289627 can be preferably employed.

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

  The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the inorganic barrier layer is provided, may be polished to improve smoothness.

  At least on the side of the substrate on which the inorganic barrier layer according to the present invention is provided, various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, or a smooth layer described later. Lamination etc. may be performed and it is preferable to perform combining the said process as needed.

[Inorganic barrier layer]
In the gas barrier film according to the present invention, at least one inorganic barrier layer is formed on a substrate. Here, the inorganic barrier layer does not need to be formed on the surface of the base material, and a base layer (smooth layer, primer layer), anchor coat layer (anchor layer), protective layer, hygroscopic layer or charged between the base material and the base material. A functional layer or the like of the prevention layer may be provided.

  The inorganic barrier layer contains an inorganic compound. Here, the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride, oxynitride or oxycarbide of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, at least one of Si and Al, Oxides, nitrides, oxynitrides or oxycarbides are preferred, and Si oxides (composition SiO), oxynitrides (composition SiON) or oxycarbides (composition SiOC) are most preferred.

  The chemical composition in the inorganic barrier layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It can also be measured by cutting the inorganic barrier layer and measuring the atomic composition ratio of the cut surface with an XPS surface analyzer. Further, the chemical composition in the inorganic barrier layer can be controlled by the type and amount of raw materials used when forming the inorganic barrier layer, conditions for forming or modifying the coating layer, and the like.

  The content of the inorganic compound contained in the inorganic barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass or more in the inorganic barrier layer. Is more preferably 98% by mass or more, and most preferably 100% by mass (that is, the inorganic barrier layer is made of an inorganic compound).

By including an inorganic compound, the inorganic barrier layer has high density and further has gas barrier properties. Here, when the gas barrier property of the inorganic barrier layer is calculated using a laminate in which the inorganic barrier layer is formed on the substrate, the water vapor transmission rate (WVTR) is 0.1 g / (m ² · day) or less. Is preferable, and it is more preferable that it is 0.01 g / (m ² · day) or less.

  The method for forming the inorganic barrier layer is not particularly limited, but a vacuum film formation method such as physical vapor deposition (PVD method) or chemical vapor deposition (CVD), or a liquid containing an inorganic compound, preferably a silicon compound And a method of reforming and forming a coating film formed by applying a liquid containing a liquid (hereinafter also simply referred to as a coating method). Of these, physical vapor deposition or chemical vapor deposition is more preferred, and chemical vapor deposition (CVD) is particularly preferred.

  Hereinafter, the vacuum film forming method and the coating method will be described.

<Vacuum deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum deposition method, and an ion plating method.

  Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate. . At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .

  The chemical vapor deposition (CVD) method is a method of depositing a film by a chemical reaction on the surface of the substrate or in the vapor phase by supplying a raw material gas containing a target thin film component onto the substrate. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.

  The inorganic barrier layer obtained by the vacuum plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, has conditions such as the metal compound (decomposition material), decomposition gas, decomposition temperature, and input power as raw materials. This is preferable because the desired compound can be produced. For details of the conditions for forming the barrier layer by the plasma CVD method, for example, the conditions described in paragraphs “0033” to “0051” of International Publication No. 2012/067186 may be appropriately employed. The inorganic barrier layer formed by such a method is preferably a layer containing an oxide, nitride, oxynitride or oxycarbide.

<Coating method>
The inorganic barrier layer according to the present invention is formed, for example, by a method (coating method) in which a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, is reformed. May be. Hereinafter, the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.

(Silicon compound)
The silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared. For example, polysilazane compounds, silazane compounds, aminosilane compounds, silylacetamide compounds, silylimidazole compounds, and other silicon compounds containing nitrogen are used.

(Polysilazane compound)
In the present invention, the polysilazane compound is a polymer having a silicon-nitrogen bond. Specifically, ceramic precursor inorganic polymers such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y have bonds such as Si—N, Si—H, and N—H in their structure. It is. In the present specification, “polysilazane compound” is also abbreviated as “polysilazane”.

  Examples of the polysilazane used in the present invention are not particularly limited and include known ones. For example, those disclosed in paragraphs “0043” to “0058” of JP2013-022799A, paragraphs “0038” to “0056” of JP2013-226758A are appropriately adopted.

  Moreover, the polysilazane compound is marketed in the solution state melt | dissolved in the organic solvent, As a commercial item of a polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310 by AZ Electronic Materials KK NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and the like.

  Another example of the polysilazane compound that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the above polysilazane (Japanese Patent Laid-Open No. 5-238827) and glycidol are reacted. Glycidol-added polysilazane (JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (JP-A-6-240208) obtained by reacting an alcohol, and metal carboxylic acid obtained by reacting a metal carboxylate Obtained by adding a salt-added polysilazane (JP-A-6-299118), an acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, and metal fine particles. Metal fine particle added Such as silazane (JP-A-7-196986), and a polysilazane compound to a ceramic at low temperatures.

(Silazane compound)
Examples of silazane compounds preferably used in the present invention include dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and 1,3-divinyl-1,1,3,3- Examples thereof include, but are not limited to, tetramethyldisilazane.

(Aminosilane compound)
Examples of aminosilane compounds preferably used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-arylaminopropyltrimethoxysilane, propylethylenediaminesilane, N- [3- (trimethoxysilyl). ) Propyl] ethylenediamine, 3-butylaminopropyltrimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, and bis (butylamino) dimethylsilane. However, it is not limited to these.

(Silylacetamide compound)
Examples of silylacetamide compounds preferably used in the present invention include N-methyl-N-trimethylsilylacetamide, N, O-bis (tert-butyldimethylsilyl) acetamide, N, O-bis (diethylhydrogensilyl) trifluoroacetamide. , N, O-bis (trimethylsilyl) acetamide, and N-trimethylsilylacetamide, but are not limited thereto.

(Silylimidazole compound)
Examples of silylimidazole compounds preferably used in the present invention include 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole, and N-trimethylsilylimidazole. However, it is not limited to these.

(Other silicon compounds containing nitrogen)
In the present invention, in addition to the above-mentioned silicon compound containing nitrogen, for example, bis (trimethylsilyl) carbodiimide, trimethylsilylazide, N, O-bis (trimethylsilyl) hydroxylamine, N, N′-bis (trimethylsilyl) urea, 3 -Bromo-1- (triisopropylsilyl) indole, 3-bromo-1- (triisopropylsilyl) pyrrole, N-methyl-N, O-bis (trimethylsilyl) hydroxylamine, 3-isocyanatopropyltriethoxysilane, and silicon Although tetraisothiocyanate etc. are used, it is not limited to these.

  Among them, polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance. Polysilazane is more preferable, and perhydropolysilazane is particularly preferable because gas barrier performance is maintained even when bent and under high temperature and high humidity conditions.

  When polysilazane is used, the content of polysilazane in the inorganic barrier layer before the modification treatment can be 100% by mass when the total mass of the inorganic barrier layer is 100% by mass. Further, when the inorganic barrier layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. Is more preferably 70% by mass or more and 95% by mass or less.

  The formation method by the coating method of the inorganic barrier layer as described above is not particularly limited, and a known method can be applied. However, an inorganic barrier layer forming coating solution containing a silicon compound and, if necessary, a catalyst in an organic solvent is used. It is preferable to apply a known wet coating method, evaporate and remove the solvent, and then perform a modification treatment.

<Modification treatment of inorganic barrier layer formed by coating method>
The modification treatment of the inorganic barrier layer formed by the coating method in the present invention refers to a conversion reaction of a silicon compound to silicon oxide or silicon oxynitride. Specifically, the gas barrier film as a whole has a gas barrier property (water vapor) The process which forms the inorganic thin film of the level which can contribute to expression of the transmittance | permeability below 1 * 10 < ^-3 > g / m < ² > * day).

  The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, formation of a silicon oxide film or a silicon oxynitride layer by a substitution reaction of a silicon compound requires a high temperature of 450 ° C. or higher, so that it is difficult to adapt to a flexible substrate such as plastic. . For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.

(Plasma treatment)
In the present invention, a known method can be used for the plasma treatment that can be used as the reforming treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms of the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

(Heat treatment)
The modification treatment can be efficiently performed by heat-treating the coating film containing the silicon compound in combination with another modification treatment, preferably an excimer irradiation treatment described later.

  In the case of forming a layer using a sol-gel method, it is preferable to use a heat treatment. The heating conditions are preferably 50 to 300 ° C., more preferably 70 to 200 ° C., preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes. Condensation is performed to form an inorganic barrier layer.

  As the heat treatment, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere by an external heater such as a resistance wire, an infrared region such as an IR heater There are no particular limitations on the method using the above light. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing a silicon compound.

  As a temperature of the coating film at the time of heat processing, it is preferable to adjust suitably in the range of 50-250 degreeC, and it is more preferable that it is the range of 50-120 degreeC.

  The heating time is preferably in the range of 1 second to 10 hours, and more preferably in the range of 10 seconds to 1 hour.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures It is.

By this ultraviolet irradiation, the base material is heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. Ceramics are promoted, and the resulting inorganic barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range where the substrate carrying the irradiated inorganic barrier layer is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by MD Excimer Co., Ltd.), UV light laser, and the like. Further, when irradiating the generated ultraviolet ray to the inorganic barrier layer, it is preferable to apply the ultraviolet ray from the generation source to the inorganic barrier layer after reflecting the ultraviolet ray from the generation source with a reflector from the viewpoint of achieving efficiency improvement and uniform irradiation. .

  The ultraviolet 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 used. For example, in the case of batch processing, a laminate having an inorganic barrier layer on the surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. In addition, when the laminate having an inorganic barrier layer on the surface is a long film, the ceramic is obtained by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while being conveyed. Can be The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and inorganic barrier layer used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

  The radiation source in the present invention may be any radiation source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. 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.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a 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.

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, sufficient reforming efficiency is obtained, and if it is 10 W / cm ² or less, it is difficult to cause ablation in the coating film and damage the substrate.

Irradiation energy amount of the VUV in the coated surface (integrated quantity of light) is preferably 10 to 10000 mJ / cm ^2, more preferably 100~8000mJ / cm ^2, a 200~6000mJ / cm ² Is more preferable. If it is 10 mJ / cm ² or more, the modification can proceed sufficiently. If it is 10,000 mJ / cm ² or less, cracking due to over-reformation and thermal deformation of the substrate are unlikely to occur.

Further, the vacuum ultraviolet light used for reforming, CO, may be generated by plasma formed in a gas containing at least one of CO ₂ and CH _4. Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

  The film composition of the inorganic barrier layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It can also be measured by cutting the inorganic barrier layer and measuring the atomic composition ratio of the cut surface with an XPS surface analyzer.

Further, the film density of the inorganic barrier layer can be appropriately set according to the purpose. For example, the film density of the inorganic barrier layer is preferably in the range of 1.5 to 2.6 g / cm ³ . If it is this range, the density of the film will be higher, and it will be difficult for the gas barrier property to deteriorate and the film to deteriorate due to humidity.

  When the inorganic barrier layer has a laminated structure of two or more layers, each inorganic barrier layer may have the same composition or a different composition. In addition, when the inorganic barrier layer has a laminated structure of two or more layers, the inorganic barrier layer may consist only of a layer formed by a vacuum film forming method or only a layer formed by a coating method. In addition, a combination of a layer formed by a vacuum film forming method and a layer formed by a coating method may be used.

  In addition, the inorganic barrier layer preferably contains a nitrogen element or a carbon element from the viewpoints of stress relaxation and absorption of ultraviolet rays used in forming a metal atom-containing layer described later. By including these elements, it has properties such as stress relaxation and ultraviolet absorption, and by improving the adhesion between the inorganic barrier layer and the metal atom-containing layer, effects such as improved gas barrier properties can be obtained. preferable.

  The chemical composition in the inorganic barrier layer can be controlled by the type and amount of the silicon compound and the like when forming the inorganic barrier layer, and the conditions when modifying the layer containing the silicon compound.

[Adhesive layer]
As shown in FIG. 1, in the gas barrier film 11 according to the present invention, an adhesive layer 14 is disposed on the surface (exposed surface) of the inorganic barrier layer 13 opposite to the substrate 12. In the optical film according to the present invention, the thickness (measured by TEM) of the adhesive layer 14 is 30 nm or less. The film thickness of the adhesive layer 14 is preferably 25 nm or less, more preferably 20 nm or less, and even more preferably less than 20 nm. Here, as the value of the film thickness of the adhesive layer 14, a value measured under the conditions described in Examples described later using a transmission electron microscope (TEM) is adopted. According to this measurement condition, when the thickness of the adhesive layer 14 is less than 20 nm (in the case of the most preferable thickness in the present invention), the presence of the adhesive layer 14 is not observed.

Here, FIG. 2 is a schematic cross-sectional view showing an embodiment of the layer structure of the gas barrier film according to the present invention. As described above, as a method for forming the adhesive layer 14 to be thin, for example, the adhesive layer 14 is formed such that a functional group such as a (meth) acryloyl group is exposed on the exposed surface of the inorganic barrier layer 13 as shown in FIG. The formation method is mentioned (FIG. 2 shows the form in which the acryloyl group is exposed). Here, by setting the film thickness of the adhesive layer 14 to 30 nm or less, the exposed (meth) acryloyl group can be sufficiently oriented on the surface of the adhesive layer 14, and the adhesive layer 14 is caused by cohesive failure. The possibility of peeling is also reduced. Further, by adopting such a configuration, it is difficult for water vapor and oxygen to enter from the side surface of the adhesive layer 14, so that the deterioration of the semiconductor nanoparticles contained in the light emitting layer 20 disposed particularly adjacently is sufficient. Can be prevented. On the other hand, when the film thickness of the adhesive layer 14 exceeds 30 nm, the influence of moisture intrusion from the side surface of the adhesive layer 14 increases in proportion to the film thickness. For example, when the adhesive layer 14 made of a silane coupling agent is thickened, it is considered that alkoxysilyl groups in the silane coupling agent are bonded to each other to form a siloxane bond and aggregate. However, the siloxane bond formed here is different from the strong bond in the SiO ₂ film and the like, and is simply connected by a bond between some incomplete functional groups with a random structure. Can cause cleavage. Therefore, when moisture permeates into such a thick adhesive layer, siloxane bonds existing in the layer are cleaved, and cohesive failure is promoted. As a result, the adhesiveness under high temperature and high humidity conditions is lowered, and the deterioration of the gas barrier property causes the deterioration of the light emitting layer.

Hereinafter, as a preferred embodiment of the present invention, a mode in which the adhesive layer 14 is formed so that a functional group such as a (meth) acryloyl group is exposed on the exposed surface of the inorganic barrier layer 13 will be described in detail. In this specification, the acryloyl group is an acyl group derived from acrylic acid represented by “CH ₂ ═CH—C (═O) —”, and the methacryloyl group is “CH ₂ ═C (CH ₃ ) -C (= O)-"is an acyl group derived from methacrylic acid, and" (meth) acryloyl group "is a collective name.

  In a preferred embodiment of this embodiment, the adhesive layer 14 is formed so that the inorganic compound constituting the inorganic barrier layer 13 and the ultraviolet curable resin constituting the light emitting layer 20 are bonded through a chemical bond. By adopting such a configuration, a strong bond is formed between the inorganic barrier layer 13 and the light emitting layer 20, so that the adhesion between these two layers is improved, and the peel strength between these two layers is increased. Can improve. Here, in this invention, it is comprised so that the peeling strength between the inorganic barrier layer 13 and the light emitting layer 20 may become 2 N / 20mm or more. The peel strength is preferably 3 N / 20 mm or more, more preferably 4 N / 20 mm or more, and further preferably 5 N / 20 mm or more. In addition, there is no restriction | limiting in particular about the upper limit of peeling strength. Here, as the value of the peel strength, a value measured by a method described in Examples described later using a peel tester FGPX-0.5 manufactured by SHIMPO is adopted.

  Here, in the adhesive layer 14 shown in FIG. 2, a reactive group other than the (meth) acryloyl group of the (meth) acryloyl group-containing compound (for example, a (meth) acryloyl group-containing silane coupling agent) (for example, ( As a result of the formation of chemical bonds (covalent bonds) with the constituent materials of the inorganic barrier layer, the (meth) acryloyl group is formed on the surface of the inorganic barrier layer. It is preferable that the adhesive layer 14 is formed by being exposed. In the present specification, a region where a functional group such as a (meth) acryloyl group above the surface of the inorganic barrier layer 13 in FIG. 2 is referred to as an “adhesive layer 14”. Here, “the functional group such as a (meth) acryloyl group is exposed on the surface of the inorganic barrier layer 13” means that the surface layer is scraped off and subjected to pyrolysis gas chromatography as described in the column of Examples described later. It is possible to confirm by taking a measurement with a graphic and comparing it with a standard.

  As described above, a reactive group other than the (meth) acryloyl group of the (meth) acryloyl group-containing compound forms a chemical bond (covalent bond) with the constituent material of the inorganic barrier layer. Examples of the (meth) acryloyl group-containing compound used in the “form in which the acryloyl group is exposed” include a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule. When the inorganic compound constituting the inorganic barrier layer 13 contains a silicon atom (for example, having a composition such as SiO, SiON, SiOC, etc.), a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule (meta ) By using as an acryloyl group-containing compound, an alkoxysilyl moiety contained in the compound can form a siloxane bond with the silicon atom. As a result, the (meth) acryloyl group contained in the compound forms a chemical bond with the silicon atom contained in the inorganic compound via another atom. By adopting such a configuration, the (meth) acryloyl group can be more firmly connected with the inorganic barrier layer, and as a result, when the ultraviolet curable resin layer is provided adjacent to the inorganic barrier layer, There is an advantage that the adhesion at the interface between these two layers can be further improved.

  Here, as the compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule, a silane coupling agent ((meth) acryloyl group-containing silane coupling agent) containing a (meth) acryloyl group is preferably used. . Examples of the (meth) acryloyl group-containing silane coupling agent include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3 -(Meth) acryloyloxypropylmethyldiethoxysilane, acrylic group-containing alkoxy oligomer and the like. Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, and KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned. One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination. In addition, “compounds containing (meth) acryloyl group and alkoxysilyl group in one molecule” other than the (meth) acryloyl group-containing silane coupling agent include, for example, polyorganosilsesquioxy introduced with (meth) acryloyl group. Sun and organic-inorganic hybrid materials such as polysiloxane-modified acrylic resins containing unsaturated double bonds. These materials may be prepared independently with reference to conventionally known knowledge, or commercially available products may be used.

  In the above, as the form in which the adhesive layer 14 is formed so that the inorganic compound constituting the inorganic barrier layer 13 and the ultraviolet curable resin constituting the light emitting layer 20 are bonded via a chemical bond, the chemical bond is “ The case where it is derived from “a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule” has been described as an example, but the functional group exposed on the surface of the adhesive layer 14 is a (meth) acryloyl group. The functional group is not limited and may be other functional groups. Examples of such a functional group include a vinyl group and an epoxy group. On the other hand, the functional group capable of forming a chemical bond with the inorganic compound constituting the inorganic barrier layer 13 is not limited to an alkoxysilyl group, but is also an alkoxysilyl group, an epoxy group, a carboxyl group, an isocyanate group, an amino group, a mercapto group. It may be a group or the like. That is, the chemical bond that constitutes the adhesive layer 14 according to the present invention has a functional group as described above instead of “a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule”. “A reactive molecule capable of forming a bond with the inorganic compound constituting the inorganic barrier layer 13 and a reactive group capable of forming a bond with the raw material of the ultraviolet curable resin constituting the light emitting layer 20 are contained in one molecule. Anything derived from "compound" can be carried out in the same manner. Examples of such compounds include vinyl group-containing silane coupling agents such as KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.) and epoxy group-containing silane coupling agents such as KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.). It is done. In addition, for example, when the functional group capable of forming a chemical bond with an inorganic compound is an isocyanate group, (meth) acryloyl group-containing isocyanate monomer and the like may be mentioned, such as Karenz (registered trademark) MOI, Karenz (registered trademark) AOI. , Karenz (registered trademark) MOI-EG, Karenz (registered trademark) BEI (manufactured by Showa Denko KK) and the like. That is, in a preferred embodiment of the present invention, “a bond is formed between the reactive group capable of forming a bond with the inorganic compound constituting the inorganic barrier layer 13 and the raw material of the ultraviolet curable resin constituting the light emitting layer 20. The compound having a reactive group that can be formed in one molecule is an alkoxysilyl group and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group, and an epoxy group. It is a silane coupling agent to be contained.

  Furthermore, as another preferred embodiment of the present invention, a mode in which the adhesive layer is composed of two or more layers (preferably two layers) is exemplified. For example, from the side adjacent to the inorganic barrier layer, a layer derived from the (meth) acryloyl group-containing silane coupling agent (first adhesive layer) and a material other than the (meth) acryloyl group-containing silane coupling agent (for example, A mode in which a layer (second adhesive layer) derived from an acrylic monomer described later is provided in this order is mentioned.

  As a method of forming the adhesive layer 14 on the surface of the inorganic barrier layer 13, a compound capable of forming the adhesive layer 14 (for example, “the inorganic barrier layer 13 is configured such as the above-described (meth) acryl group-containing silane coupling agent”). A compound having a reactive group capable of forming a bond with an inorganic compound and a reactive group capable of forming a bond with the raw material of the ultraviolet curable resin constituting the light emitting layer 20 in a single molecule ") An example is a method in which the dissolved solution is applied to the surface of the inorganic barrier layer 13 and dried. In this case, examples of the solvent that can be used include toluene, xylene, and other high-boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; Examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol; ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and diethylene glycol monomethyl ether.

  Here, when the inorganic compound constituting the inorganic barrier layer 13 contains a silicon atom, “functional group such as (meth) acryloyl group” such as silane coupling agent containing functional group such as (meth) acryloyl group and the like When the adhesive layer is formed using the “compound containing an alkoxysilyl group in one molecule”, the “compound containing a functional group such as a (meth) acryloyl group and an alkoxysilyl group in one molecule” as time passes. The contained alkoxysilyl group causes a hydrolysis / condensation reaction with the silicon atom contained in the inorganic compound. As a result, a functional group such as a (meth) acryloyl group contained in “a compound containing a functional group such as a (meth) acryloyl group and an alkoxysilyl group in one molecule” is contained in the inorganic compound via another atom. A chemical bond is formed with the silicon atom.

  Moreover, when the inorganic compound which comprises the inorganic barrier layer 13 contains a silicon atom, it is hydrophilic on the surface of the inorganic barrier layer 13 for the purpose of increasing the reaction point on the inorganic barrier layer 13 side where the hydrolysis / condensation reaction described above occurs. It is preferable to form an adhesive layer using a “compound containing a functional group such as a (meth) acryloyl group and an alkoxysilyl group in one molecule” after the formation treatment. Here, examples of the surface hydrophilization treatment that can be performed to increase the reaction point include an oxygen plasma treatment, a corona treatment, an excimer (vacuum ultraviolet) treatment, and a UV ozone treatment. There is no restriction | limiting in particular about the specific method for performing these surface hydrophilization processes, A conventionally well-known knowledge can be referred suitably. When such surface hydrophilization treatment is performed, the surface of the inorganic barrier layer is hydrophilized. For example, when the inorganic compound constituting the inorganic barrier layer contains a silicon atom, a large number of silanol groups (—Si—OH groups) are present. It forms on the surface of the inorganic barrier layer. When an adhesive layer is formed in this state, silanol groups are included in “compounds containing (meth) acryloyl groups and alkoxysilyl groups in one molecule” such as silane coupling agents containing functional groups such as (meth) acryloyl groups. By reacting with the alkoxysilyl group, the number (density) of functional groups such as (meth) acryloyl groups exposed on the surface of the inorganic barrier layer can be increased. As a result, when the light emitting layer is provided so as to be adjacent to the inorganic barrier layer, there is an advantage that the adhesion at the interface between these two layers can be further improved.

  In the above, “(meth) acryloyl as a result of forming a chemical bond (covalent bond) with a constituent material of the inorganic barrier layer by a reactive group other than the (meth) acryloyl group of the (meth) acryloyl group-containing compound. Although the embodiment of the present invention has been described in detail for the “form in which the group is exposed”, the present invention is not limited to such a form. For example, “a compound containing a functional group such as a (meth) acryloyl group is attached to the surface of the inorganic barrier layer 13 without a chemical bond, and as a result, a functional group such as a (meth) acryloyl group is exposed. Form "may be sufficient. Examples of the (meth) acryloyl group-containing compound used in such a form include compounds other than the above-described (meth) acryloyl group-containing silane coupling agent among compounds containing a (meth) acryloyl group.

  Examples of the (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent include polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. .

Polyol poly (meth) acrylate is an ester compound of polyol and (meth) acrylic acid. The polyol selected here is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4 -Chain aliphatic polyols such as diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol, hydrogenated polyolefin polyol, and more, 1,4-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, tricyclo [5.2.1.0 ^{2, 6]} Dekanji Examples include polyols having an alicyclic structure such as butanol, 2-methylcyclohexane-1,1-dimethanol, and further trimer triol, p-xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct And polyols having an aromatic ring such as biphenolethylene oxide adduct, and further polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and further, polyhexamethylene adipate and polyhexamethylene. Examples include polyester polyols such as succinate and polycaprolactone, and α, ω-poly (1,6-hexylene carbonate) diol, α, ω-poly (3-methyl-1,5- Acetylene carbonate) diol, α, ω-poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, α, ω-poly [(1,9-nonylene: 2-methyl-1,8 (Octylene) carbonate] (poly) carbonate diols such as diols. These may be used alone or in combination of two or more.

  Epoxy (meth) acrylate is a compound obtained by adding (meth) acrylic acid to the terminal epoxy group of an epoxy resin. There is no restriction | limiting in particular in the epoxy resin selected in this case. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.

  Urethane (meth) acrylate is a compound obtained by reacting a polyol and a polyisocyanate with a hydroxyl group-containing (meth) acrylate, or a polyol and an isocyanate group-containing (meth) acrylate. There are no particular restrictions on the polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, and isocyanato group-containing (meth) acrylate selected at this time. The polyol is the same as the polyol used in the polyol poly (meth) acrylate. Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. And the like. These may be used alone or in combination of two or more. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples include butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylamide. These may be used alone or in combination of two or more. Examples of the isocyanato group-containing (meth) acrylate include 2-isocyanatoethyl (meth) acrylate. These may be used alone or in combination of two or more.

  The (meth) acrylic monomer is a compound obtained by removing the polyol poly (meth) acrylate, the epoxy (meth) acrylate, and the urethane (meth) acrylate from the above-described (meth) acryloyl group-containing compound.

  Examples of (meth) acrylic monomers include (meth) acryloyl-containing compounds having a cyclic ether group such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and di Cyclic fats such as cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanylethyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate Monofunctional (meth) acryloyl group-containing compound having a group, lauryl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylic , Tert-butyl (meth) acrylate, isooctyl (meth) acrylate, monofunctional (meth) acryloyl group-containing compounds having a chain aliphatic group such as isoamyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl ( Monofunctional (meth) acryloyl group-containing compound having an aromatic ring such as (meth) acrylate, polyethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, nonanediol di (meth) acrylate, hexanediol di (meth) acrylate , Tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaeri Ritorupenta (meth) acrylate, and polyfunctional (meth) acryloyl group-containing compounds such as dipentaerythritol hexa (meth) acrylate. In the present specification, the monofunctional (polyfunctional) (meth) acryloyl group-containing compound is also simply referred to as “monofunctional (polyfunctional) (meth) acrylate compound”.

  The (meth) acryloyl group is exposed on the surface of the inorganic barrier layer 13 by attaching a (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent as described above to the surface of the inorganic barrier layer 13. Examples of the method include a method in which a solution obtained by dissolving the (meth) acryloyl group-containing compound in an appropriate solvent such as those described above is applied to the surface of the inorganic barrier layer 13 and dried. At this time, a suitable photopolymerization initiator is added to the solution, and the coating obtained by applying the solution and drying is subjected to a light irradiation treatment, and a part of the (meth) acryloyl group-containing compound. May be polymerized. However, if the polymerization is complete, the unreacted (meth) acryloyl group contained in the adhesive layer disappears, so the polymerization should not be performed completely.

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays. Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. Moreover, a metallocene compound can also be used as a photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, the said solution may contain a filler for the purpose of slipperiness and winding-up property. Examples of the filler include silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, anhydrous silica, fused silica, crystalline silica, and ultrafine powder amorphous silica; titanium oxide, zinc oxide, zirconium oxide, niobium oxide And metal oxide inorganic fillers such as aluminum oxide, cerium oxide, and yttrium oxide. Among these, silica-based inorganic fillers are particularly preferable. Further, the shape of the filler is preferably spherical, and the particle size is preferably in the range of 10 to 50 μm.

  The content of the (meth) acryloyl group-containing compound is preferably 80 to 100% by mass with respect to 100% by mass of the solid content contained in the solution obtained by dissolving the (meth) acryloyl group-containing compound in a solvent. The content of the polymerization initiator is preferably 0 to 5% by mass, and the content of the filler is preferably 0 to 20% by mass.

[Other parts]
The gas barrier film according to an embodiment of the present invention essentially includes a substrate, an inorganic barrier layer, and an adhesive layer, but may further include other members. The gas barrier film according to this embodiment is formed, for example, between a base material and an inorganic barrier layer; between the inorganic barrier layers (when a plurality of inorganic barrier layers are present); or the base material inorganic barrier layer is formed. You may have another member in the surface which is not.

  Here, the other members are not particularly limited, and members used for conventional gas barrier films can be used similarly or appropriately modified. Specific examples include a base layer (smooth layer, primer layer), an anchor coat layer (anchor layer), a bleed-out prevention layer, a protective layer, a functional layer such as a moisture absorption layer and an antistatic layer, and the like. The other members may be used alone or in combination of two or more. Moreover, the other member may exist as a single layer or may have a laminated structure of two or more layers.

  Instead of the above or in addition to the above, the inorganic barrier layer may exist as a single layer (a layer that can be produced in one step) or may have a laminated structure of two or more layers. By providing a plurality of layers, the gas barrier property can be further improved. In the latter case, one or more inorganic barrier layers may exist as one unit, or two or more of the above units may be laminated.

[Underlayer (smooth layer, primer layer)]
The gas barrier film according to the present invention may have a base layer (smooth layer, primer layer) between the base material and the inorganic barrier layer, for example. The underlayer is provided for flattening the rough surface of the substrate on which protrusions and the like exist, or for filling the unevenness and pinholes generated in the inorganic barrier layer with the protrusions existing on the substrate to flatten the surface. . Such an underlayer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably includes a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further has an underlayer containing a carbon-containing polymer between the base material and the inorganic barrier layer.

  The underlayer also contains a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material or the like with an active energy ray such as an ultraviolet ray to be cured is heated. And thermosetting resins obtained by curing. These curable resins may be used alone or in combination of two or more.

  As an active energy ray curable material used for forming the underlayer, specifically, UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation (polymerizable unsaturated group on silica fine particles) And a compound obtained by bonding an organic compound having a compound (a). Further, as thermosetting materials, specifically, TutProm series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, manufactured by DIC Corporation Unidic (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd. Company-made inorganic / organic nanocomposite material SSG coat, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin Butter, and the like can be mentioned.

  The smoothness of the underlayer is a value expressed by the surface roughness specified in JIS B 0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less.

  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.

  Although it does not restrict | limit especially as thickness of a base layer, The range of 0.1-10 micrometers is preferable.

[Anchor coat layer (anchor layer)]
On the surface of the substrate according to the present invention, an anchor coat layer (anchor layer) may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

[Bleed-out prevention layer]
The gas barrier film according to the present invention may further have a bleed-out preventing layer. The bleed-out prevention layer is a base (smooth) for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base to the surface when the film having the base layer is heated and contaminates the contact surface. ) Provided on the opposite side of the substrate having the layer. The bleed-out prevention layer may basically have the same configuration as the base (smooth) layer as long as it has this function.

  Compounds that can be included in the bleed-out prevention layer include polyunsaturated organic compounds having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated group in the molecule. Hard coat agents such as unitary unsaturated organic compounds can be mentioned.

  The thickness of the bleed-out prevention layer is 1 to 10 μm, preferably 2 to 7 μm.

<Light emitting layer>
The light emitting layer 20 usually includes semiconductor nanoparticles that function as quantum dots and an ultraviolet curable resin (cured product of an ultraviolet curable resin).

  “Semiconductor nanoparticles” refer to fine particles having a quantum confinement effect (quantum dot effect) composed of a crystal of a semiconductor material and having a size of several nanometers to several tens of nanometers. The energy level E of such semiconductor nanoparticles is generally expressed by the following formula (1) when the Planck constant is “h”, the effective mass of electrons is “m”, and the radius of the semiconductor nanoparticles is “R”. expressed.

Formula (1) E∝h ² / mR ²
As shown in Formula (1), the band gap of the semiconductor nanoparticles increases in proportion to “R ⁻² ” (so-called quantum confinement effect). In this way, by controlling and defining the particle diameter of the semiconductor nanoparticles, the band gap value of the semiconductor nanoparticles can be controlled, and diversity that does not exist in ordinary atoms can be provided. Therefore, it can be excited by light, or converted into light having a desired wavelength and emitted. In this embodiment, such luminescent semiconductor nanoparticles are used as a luminescent material of the luminescent layer.

  In this embodiment, the content of the semiconductor nanoparticles contained in the light emitting layer is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and 2.0% with respect to the total mass of the light emitting layer. More preferred is ˜25% by mass. If the content is 0.01% by mass or more, sufficient luminance can be obtained, and if it is 50% by mass or less, an appropriate inter-particle distance of the semiconductor nanoparticles is maintained in the quantum dot layer (light emitting layer). And the quantum size effect can be sufficiently exerted.

  The average particle diameter of the semiconductor nanoparticles is about several nm to several tens of nm as described above, but is set to an average particle diameter corresponding to the target emission color. For example, when it is desired to obtain red light emission, the average particle diameter of the semiconductor nanoparticles is preferably 3.0 to 20 nm, and when it is desired to obtain green light emission, it is preferably 1.5 to 10 nm. When it is desired to obtain blue light emission, the thickness is preferably 1.0 to 3.0 nm.

  In the present specification, the size (particle diameter) of the semiconductor nanoparticles is the shell region or the surface when the semiconductor nanoparticles have a core / shell structure as described later, or are modified with a surface modifier. It means the total size including the region composed of the modifier.

  As a method for measuring the average particle diameter, a known method can be used. For example, a method of observing semiconductor nanoparticles using a transmission electron microscope (TEM) and obtaining the number average particle size of the particle size distribution therefrom, or a method of obtaining an average particle size using an atomic force microscope (AFM) The particle size can be measured using a particle size measuring apparatus using a dynamic light scattering method, for example, “ZETASIZER Nano Series Nano-ZS” manufactured by Malvern. In addition, a method of deriving the particle size distribution from the spectrum obtained by the X-ray small angle scattering method using the particle size distribution simulation calculation of the semiconductor nanoparticles can be used. In addition, the average particle diameter of the semiconductor nanoparticle in this specification shall mean the average value of the particle diameter of 300 particle | grains observed using atomic force microscope (AFM).

  In this embodiment, the average aspect ratio (major axis diameter / minor axis diameter) of the semiconductor nanoparticles is preferably 1.0 to 2.0, and preferably 1.1 to 1.7. Is more preferable. In addition, the average aspect ratio of the semiconductor nanoparticles in this specification means the average value of the aspect values of 300 particles observed using an atomic force microscope (AFM).

(1) Constituent material of semiconductor nanoparticles As constituent materials of semiconductor nanoparticles, for example, a simple substance of Group 14 element of periodic table such as carbon, silicon, germanium, tin, etc., Group 15 of periodic table such as phosphorus (black phosphorus), etc. Elemental element simple substance, periodic table group 16 element such as selenium, tellurium, etc., compound consisting of a plurality of periodic table group 14 elements such as silicon carbide (SiC), tin (IV) oxide (SnO ₂ ), tin sulfide ( II, IV) (Sn (II) Sn (IV) S ₃ ), tin sulfide (IV) (SnS ₂ ), tin sulfide (II) (SnS), tin selenide (II) (SnSe), tin telluride ( II) (SnTe), lead sulfide (II) (PbS), lead selenide (II) (PbSe), lead telluride (II) (PbTe) periodic table group 14 elements and periodic table group 16 elements Compounds of boron nitride (BN), lithium Boron nitride (BP), Boron arsenide (BAs), Aluminum nitride (AlN), Aluminum phosphide (AlP), Aluminum arsenide (AlAs), Aluminum antimonide (AlSb), Gallium nitride (GaN), Gallium phosphide Periodic tables of (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), etc. A compound of a group element and a group 15 element of the periodic table (or a group III-V compound semiconductor), aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), gallium selenide _(Ga 2 _Se 3), telluride gallium _(Ga 2 _Te 3), acid Indium _{(In 2 O} 3), indium sulfide _{(In 2 S} 3), indium selenide _(In 2 _Se 3), periodic table Group 13 element and Periodic Table Group 16 such as a telluride, indium _(In 2 Te ₃₎ A compound with an element, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI), etc. Compound, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe), etc. Objects (or II-VI compound semiconductor), arsenic sulfide _{(III) (As 2 S} 3), selenium arsenic _(III) (As 2 _Se 3), tellurium arsenic _(III) (As 2 _Te 3), sulfide Antimony (III) (Sb ₂ S ₃ ), antimony selenide (III) (Sb ₂ Se ₃ ), antimony telluride (III) (Sb ₂ Te ₃ ), bismuth sulfide (III) (Bi ₂ S ₃ ), selenium Compounds of periodic table group 15 elements and periodic table group 16 elements such as bismuth (III) iodide (Bi ₂ Se ₃ ) and bismuth telluride (III) (Bi ₂ Te ₃ ), copper oxide (I) (Cu ₂ O), copper (I) selenide (Cu ₂ Se) and other compounds of Group 11 elements and Group 16 elements of the periodic table, copper chloride (I) (CuCl), copper bromide (I) ( CuBr), copper iodide (I (CuI), silver chloride (AgCl), periodic table group 11 elements such as silver bromide (AgBr) and group 17 elements, periodic table group 10 such as nickel oxide (II) (NiO) Compound of element and group 16 element of periodic table, compound of group 9 element of periodic table and group 16 element of periodic table such as cobalt (II) oxide (CoO), cobalt sulfide (II) (CoS), tetraoxide Compounds of Group 8 elements of the periodic table such as triiron (Fe ₃ O ₄ ) and iron sulfide (II) (FeS) and Group 16 elements of the periodic table, Periodic Table 7 of manganese (II) oxide (MnO), etc. Compounds of group elements and group 16 elements of the periodic table, compounds of group 6 elements of the periodic table and group 16 elements of the periodic table such as molybdenum sulfide (IV) (MoS ₂ ), tungsten oxide (IV) (WO ₂ ), etc. , Vanadium oxide (II) (VO), vanadium oxide (IV) _(VO 2), compounds of the periodic table group 5 element and the periodic table group 16 element such as tantalum oxide _{(V) (Ta 2 O 5} ), titanium oxide _{(TiO 2, Ti 2 O 5} , Ti 2 O 3 , Ti ₅ O ₉ etc.) periodic table group 4 element and periodic table group 16 element compound, periodic table group 2 element such as magnesium sulfide (MgS), magnesium selenide (MgSe) and periodic table Compounds with group 16 elements, cadmium (II) chromium (III) (CdCr ₂ O ₄ ), cadmium selenide (II) chromium (III) (CdCr ₂ Se ₄ ), copper (II) chromium (III) sulfide (III) ( CuCr ₂ S _4), chalcogen spinels such as mercury selenide (II) chromium _{(III) (HgCr 2 Se 4} ), although barium titanate (BaTiO ₃₎ can be mentioned, _SnS 2, S Compounds of Group 14 elements of the periodic table such as S, SnSe, SnTe, PbS, PbSe, PbTe, and Group 16 elements of the periodic table, III-V such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc. Group 13 semiconductors such as Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ Compounds of group elements and group 16 elements of the periodic table, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe and other II-VI group compound semiconductors, As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te ₃ periodic table group 15 element and periodic table group 16 element compound, MgS, MgSe periodic table group 2 element and periodic table group 16 element Compounds. Among these, Si, Ge, GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO, and CdS are more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and because a pure spectrum can be stably obtained in the visible light region, optical devices Is advantageous for the formation of In particular, CdSe, ZnSe, and CdS are preferable from the viewpoint of light emission stability, and ZnO and ZnS are preferable from the viewpoint of light emission efficiency, high refractive index, safety, and economy. In addition, these light emitting materials may be used individually by 1 type, and may be used in combination of 2 or more type.

  The semiconductor nanoparticles described above can be doped with a small amount of various elements as impurities as necessary. By adding such a doping substance, the emission characteristics can be greatly improved.

  In the present invention, the band gap refers to the energy difference between the valence band of the semiconductor nanoparticles and the conductor. The emission wavelength (nm) of the semiconductor nanoparticles is represented by emission wavelength (nm) = 1240 / band gap (eV). The band gap (eV) of the semiconductor nanoparticles can be obtained using a Tauc plot. Hereinafter, the Tauc plot, which is one of the optical scientific measurement methods of the band gap (eV), will be described.

First, the measurement principle of the band gap (E ₀ ) using the Tauc plot is shown below.

In the region of relatively large absorption near the optical absorption edge on the long wavelength side of the semiconductor material, between the light absorption coefficient α and the light energy hν (where h is the Planck constant and ν is the frequency) and the band cap energy E ₀ It is considered that the following equation (A) holds.

Formula (A)
αhν = B (hν−E ₀ ) ²
Therefore, an absorption spectrum is measured, and hν is plotted (so-called Tauc plot) with respect to (αhν) raised to the 0.5th power, and the value of hν at α = 0 obtained by extrapolating the straight section is sought. The band gap energy E ₀ of the semiconductor nanoparticles is obtained. In the case of semiconductor nanoparticles, since the difference between absorption and emission spectra (Stokes shift) is small and the waveform is sharp, the maximum wavelength of the emission spectrum can be used as an index of the band gap.

  In addition to the above methods, the methods for estimating the energy levels of these materials include a method for obtaining energy levels obtained by scanning tunneling spectroscopy, ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and There is a method of optically estimating the band gap.

  The semiconductor nanoparticles according to this embodiment preferably have an inorganic coating layer or a coating composed of an organic ligand. That is, the semiconductor nanoparticles according to the present embodiment include a core region composed of the materials listed in the above “(1) Constituent material of semiconductor nanoparticles” and a shell region composed of an inorganic coating layer or an organic ligand. It is preferable to have a core-shell structure having

  The core / shell structure is preferably formed of at least two kinds of compounds, and may form a gradient structure (gradient structure) composed of two or more kinds of compounds. As a result, in the coating liquid for forming the light emitting layer (hereinafter, also referred to as “light emitting layer forming coating liquid”), aggregation of the semiconductor nanoparticles can be effectively prevented, and the dispersibility of the semiconductor nanoparticles can be prevented. In addition, the luminance efficiency is improved, and the occurrence of color misregistration can be suppressed when an optical device including the quantum dot layer (light emitting layer) according to this embodiment is continuously driven. Further, the light emission characteristics can be stably obtained due to the presence of the shell region. In addition, when the semiconductor nanoparticles have a shell region on the surface, a surface modifier as described later can be reliably supported near the surface of the semiconductor nanoparticles. Although the thickness of a shell area | region is not specifically limited, 0.1-10 nm is preferable and 0.1-5 nm is more preferable.

  In general, the emission color of semiconductor nanoparticles can be controlled by the average particle diameter. When the thickness of the shell region is within the above range (thickness corresponding to several atoms to a thickness less than one semiconductor nanoparticle), the semiconductor nanoparticles are densely contained in the quantum dot layer (light emitting layer). And a sufficient amount of light emission can be obtained. Further, due to the presence of the shell region, it is possible to suppress the transfer of non-emission electron energy due to the defects existing on the surfaces of the core regions and the electron traps on the dangling bonds, and the decrease in quantum efficiency can be suppressed.

(2) Surface modifier It is preferable that the semiconductor nanoparticle of this form has a surface modifier in the surface vicinity. Thereby, the dispersion stability of the semiconductor nanoparticles in the light emitting layer forming coating solution can be made particularly excellent. In addition, by having a surface modifier, the shape of the semiconductor nanoparticles has a high sphericity, and the particle size distribution of the semiconductor nanoparticles can be kept narrow, so that its light emission characteristics are particularly excellent. Can do.

  The functional surface modifier that can be applied in the present invention may be one directly attached to the surface of the semiconductor nanoparticles, or one attached via a shell (the surface modifier is directly attached to the shell). And may not be in contact with the core of the semiconductor nanoparticles.

  Examples of the surface modifier include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, and the like. Trialkylphosphines; polyoxyethylene alkylphenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; tri (n-hexyl) amine, tri (n-octyl) amine, tri ( Tertiary amines such as n-decyl) amine; tripropylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide Organic phosphorus compounds such as tridecylphosphine oxide; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; organic nitrogen compounds such as nitrogen-containing aromatic compounds such as pyridine, lutidine, collidine and quinolines; hexylamine and octyl Aminoalkanes such as amine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine; dialkyl sulfides such as dibutyl sulfide; dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide; sulfur-containing aromatic compounds such as thiophene Organic sulfur compounds such as: higher fatty acids such as palmitic acid, stearic acid and oleic acid; alcohols; sorbitan fatty acid esters; fatty acid-modified polyesters Ethers; tertiary amine-modified polyurethanes, polyethylene imines, and the like. When the semiconductor nanoparticles are prepared by a method as described later, the surface modifier is preferably a substance that coordinates and stabilizes in the fine particles constituting the semiconductor nanoparticles in a high-temperature liquid phase. Specifically, trialkylphosphines, organic phosphorus compounds, aminoalkanes, tertiary amines, organic nitrogen compounds, dialkyl sulfides, dialkyl sulfoxides, organic sulfur compounds, higher fatty acids, and alcohols are preferable. By using such a surface modifier, the dispersibility of the semiconductor nanoparticles in the light emitting layer forming coating solution can be made particularly excellent. Further, the shape can be made higher in sphericity, the particle size distribution can be made sharper, and the light emission characteristics of the semiconductor nanoparticles can be made particularly excellent.

(3) Manufacturing method of semiconductor nanoparticle As a manufacturing method of a semiconductor nanoparticle, the conventionally well-known method (The manufacturing method under a high vacuum, the manufacturing method in a liquid phase, etc.) can be used suitably. Moreover, it can also be purchased as a commercial item from Aldrich, CrystalPlex, NNLab, etc.

  For example, as a production method under high vacuum, a molecular beam epitaxy method, a CVD method, etc .; as a production method in a liquid phase, an aqueous raw material is used, for example, alkanes such as n-heptane, n-octane, isooctane, or benzene , A reverse micelle method in which crystals are grown in a reverse micelle phase in a non-polar organic solvent such as an aromatic hydrocarbon such as toluene and xylene, and a thermally decomposable raw material as a high-temperature liquid-phase organic medium. Examples thereof include a hot soap method in which crystal growth is performed by injection, and a solution reaction method in which crystal growth is performed at a relatively low temperature using an acid-base reaction as a driving force, as in the hot soap method. Any method can be used from these production methods, and among these, a production method in a liquid phase is preferable. It is possible to exchange with the functional surface modifier described above by an exchange reaction performed in the liquid phase.

(UV curable resin)
In the quantum dot layer (light emitting layer) according to this embodiment, the ultraviolet curable resin functions as a matrix for dispersing the semiconductor nanoparticles. An ultraviolet curable resin is used as a raw material for the ultraviolet curable resin used in this embodiment.

  Examples of ultraviolet curable resins include urethane (meth) acrylate resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, acrylic resins such as polyol (meth) acrylate resins, or epoxy resins. Specific examples of these include, as a constituent material of the adhesive layer, the above-mentioned “(meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent” (that is, polyol poly (meth) acrylate, And materials such as epoxy (meth) acrylate, urethane (meth) acrylate, (meth) acrylic monomer). Among these, from the viewpoint of gas permeation suppression (gas permeation from the sheet end face) and the adhesion between the inorganic barrier layer surface, an epoxy (meth) acrylate resin (for example, Unidic (registered trademark) V-5500 ( DIC Corporation)) and urethane (meth) acrylate resins are preferably used. In addition, when the ultraviolet curable resin that is a raw material of the ultraviolet curable resin constituting the light emitting layer contains an epoxy resin, the above-mentioned “reactive group capable of forming a bond with an inorganic compound and the raw material of the ultraviolet curable resin” The “reactive group capable of forming a bond with the raw material of the ultraviolet curable resin” in the “compound having a reactive group capable of forming a bond in the molecule” is preferably an epoxy group. Similarly, when the ultraviolet curable resin that is a raw material of the ultraviolet curable resin constituting the light emitting layer contains an acrylic resin, the above-mentioned “reactive group capable of forming a bond with an inorganic compound and the raw material of the ultraviolet curable resin” The “reactive group capable of forming a bond with the raw material of the ultraviolet curable resin” in the “compound having a reactive group capable of forming a bond with itself in a molecule” is preferably a (meth) acryloyl group. The latter form is more preferably employed from the viewpoint of making the effects of the present invention appear more remarkably.

  Further, as the photopolymerization initiator of the ultraviolet curable resin, the materials described above as the constituent material of the adhesive layer can be similarly used.

  The thickness of the quantum dot layer (light emitting layer) according to this embodiment is not particularly limited, but is preferably 10 to 500 μm, and more preferably 30 to 300 μm. When the thickness of the quantum dot layer (light emitting layer) is 10 μm or more, it is easy to adjust the light emission balance of B, G, R, and good color gamut reproducibility can be obtained. On the other hand, when the thickness of the quantum dot layer (light emitting layer) is 500 μm or less, the quantum dot layer (light emitting layer) can be efficiently cured, and good productivity can be obtained.

≪Method for manufacturing optical film≫
Although there is no restriction | limiting in particular about the manufacturing method (namely, the formation method of a light emitting layer) which concerns on this invention, As a preferable manufacturing method, a pair of gas barrier films which have the structure mentioned above are used, and a semiconductor nanoparticle and ultraviolet curing type A step of producing a laminated body by sandwiching a light emitting layer precursor containing a resin (laminated body producing step), and a step of irradiating the laminated body with ultraviolet rays to cure the ultraviolet curable resin to form an ultraviolet curable resin ( And an ultraviolet irradiation step). Under the present circumstances, the optical film which concerns on this invention can be manufactured by performing so that the said contact bonding layer and the said light emitting layer precursor may contact | connect. In particular, a light emitting layer forming coating solution containing semiconductor nanoparticles and an ultraviolet curable resin (resin component and photopolymerization initiator) is applied to the surface of the adhesive layer of the gas barrier film according to the present invention, and then dried to emit light. A layer precursor is formed, and another gas barrier film according to the present invention is laminated so that the adhesive layer is adjacent to the light emitting layer precursor. Finally, the obtained laminate is subjected to ultraviolet irradiation treatment. By applying, at the same time as forming the light emitting layer, a laminate (optical film according to the present invention) in which the light emitting layer is sandwiched between two gas barrier films according to the present invention can be obtained.

  There are no particular limitations on the specific method of ultraviolet irradiation treatment and the conditions at that time, and it is possible to appropriately select the method and conditions while referring to conventionally known knowledge.

  The optical film obtained as described above can be applied to various optical devices. That is, according to one form of this invention, an optical device provided with the said optical film is provided. The optical film according to the present invention can be used as, for example, a high brightness film disposed between a light source and a polarizing plate in a liquid crystal display (LCD).

  The optical film according to the present invention suppresses a decrease in gas barrier properties between the inorganic barrier layer and the light emitting layer adjacent thereto when placed under a high temperature and high humidity condition. As a result, deterioration of the semiconductor nanoparticles contained in the light emitting layer can be suppressed, and as a result, a decrease in luminance of the optical film itself can be prevented.

  The present invention will be specifically described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively. Further, in the following examples, unless otherwise specified, the operation was performed under conditions of room temperature (25 ° C.) / Relative humidity 40 to 50%.

<< Production of gas barrier film >>
[Preparation of gas barrier film 1]
(Preparation of base material)
A polyethylene terephthalate (PET) film with a double-sided easy-adhesion layer having a thickness of 50 μm (manufactured by Teijin DuPont Films Ltd., KEL86W) was used as a substrate.

(Formation of underlayer)
JSR Co., Ltd. UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) Z7501 diluted with butyl acetate to a solid content concentration of 35% is coated with the above-mentioned base material so that the dry film thickness becomes 2 μm. After coating on the easy-adhesive surface side with a bar coater, drying was performed at 80 ° C. for 2 minutes as a drying condition. Next, under an air atmosphere, ultraviolet irradiation treatment was performed with a high-pressure mercury lamp under conditions of 700 mW / cm ² and 250 mJ / cm ² to form an underlayer.

(Formation of inorganic barrier layer: sputtering method)
The laminated film of the base material and the underlayer obtained above was placed in a take-up magnetron sputtering apparatus and evacuated to 3 × 10 ⁻⁶ Torr. Thereafter, the laminated film was rolled back, sufficiently degassed, and it was confirmed that there was no fluctuation in moisture pressure even when the laminated film was conveyed. Here, a B-doped Si target was used as a sputtering target. Thereafter, an O ₂ / Ar mixed gas (O ₂ / Ar = 30/100 (volume%)) was introduced into the tank at 100 sccm. After maintaining the pressure at 8.0 × 10 ⁻⁴ Torr, the main roll temperature is set to room temperature, the input power density is set to 1 W / cm ² , and the film speed is set to Vf = 1.0 m / min. An inorganic barrier layer (composition SiO _x ) having a thickness of 150 nm was formed.

(Inorganic barrier layer surface hydrophilization treatment (oxygen plasma treatment))
The exposed surface of the inorganic barrier layer formed as described above was subjected to surface hydrophilization treatment (oxygen plasma treatment) by the following method.

(Surface hydrophilization treatment: oxygen plasma treatment)
Using an atmospheric pressure plasma apparatus (manufactured by Well Co., Ltd.), nitrogen gas is introduced as a discharge gas, the oxygen concentration is controlled to 1% by volume, the frequency of 5 kHz, and the applied power of 5 kV. Surface hydrophilization treatment (oxygen plasma treatment) was performed.

(Formation of adhesive layer: acrylic resin + acryloyl group-containing silane coupling agent)
Solid content of 50% by mass of dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, and 50% by mass of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an acryloyl group-containing silane coupling agent, is obtained with propylene glycol monomethyl ether (PGME). A coating solution for forming an adhesive layer was prepared by diluting to a solid content concentration of 1%. Next, the adhesive layer forming coating solution was applied to the exposed surface of the inorganic barrier layer with a bar coater so that the dry film thickness was 30 nm (value observed with TEM), and then dried at 80 ° C. for 1 minute. Was dried. Next, an adhesive layer was formed by performing an ultraviolet irradiation treatment with a high-pressure mercury lamp under conditions of 500 mW / cm ² and 200 mJ / cm ^{2 in} an air atmosphere, and a gas barrier film 1 was produced. In addition, the surface layer on the inorganic barrier layer side of the gas barrier film 1 is scraped off, measured by pyrolysis gas chromatography, and checked with the standard, so that the acryloyl group is exposed on the exposed surface of the adhesive layer. It was confirmed. Moreover, the measurement conditions of TEM for measuring the dry film thickness of an adhesive layer are as follows.

(TEM measurement conditions)
Device: JEOL JEM-2010F
Accelerating voltage: 200kV
Pretreatment: flake processing by FIB processing.

[Preparation of gas barrier film 2]
A gas barrier film 2 was prepared by the same method as the preparation of the gas barrier film 1 described above, except that the adhesive layer was formed by the following method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 2.

(Formation of adhesive layer: acryloyl group-containing organic-inorganic hybrid material)
A coating solution obtained by diluting KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic equivalent 210 g / mol) with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% is an organic-inorganic hybrid material containing an acryloyl group and a methoxy group. The dried film thickness was applied to the exposed surface of the inorganic barrier layer with a bar coater so as to be 30 nm (value observed with TEM). Then, the adhesive layer which consists of the said organic-inorganic hybrid material was formed by drying at 80 degreeC for 1 minute, and the gas barrier film 2 was produced. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 2.

[Preparation of gas barrier film 3]
The application amount of the coating liquid at the time of forming the adhesive layer was the same as that of the gas barrier film 2 described above except that the dry film thickness of the adhesive layer was changed to 20 nm (value observed with TEM). The gas barrier film 3 was produced by the method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 3.

[Preparation of gas barrier film 4]
The gas barrier was formed by the same method as that for the gas barrier film 2 described above except that the coating amount of the coating liquid when forming the adhesive layer was changed so that the dry film thickness of the adhesive layer was 15 nm as a theoretical value. Film 4 was produced. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 4. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

[Preparation of gas barrier film 5]
In the formation of the adhesive layer, the gas barrier film 4 described above except that KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an acryloyl group-containing silane coupling agent, was used instead of KR-513, which is an organic-inorganic hybrid material. A gas barrier film 5 was produced in the same manner as in the above. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 5. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

[Preparation of gas barrier film 6]
In the formation of the adhesive layer, the gas barrier film 4 described above except that KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) which is a methacryloyl group-containing silane coupling agent is used instead of KR-513 which is an organic-inorganic hybrid material. A gas barrier film 6 was produced in the same manner as in the above. In addition, it confirmed that the methacryloyl group was exposed on the exposed surface of the contact bonding layer of the gas-barrier film 6 similarly to the above. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

[Preparation of gas barrier film 7]
In the formation of the adhesive layer, the gas barrier film 4 described above except that KBM-1003 (made by Shin-Etsu Chemical Co., Ltd.) which is a vinyl group-containing silane coupling agent is used instead of KR-513 which is an organic-inorganic hybrid material. A gas barrier film 7 was produced in the same manner as in the above. It was confirmed in the same manner as above that the vinyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 7. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

[Preparation of gas barrier film 8]
A gas barrier film 8 was produced by the same method as the production of the gas barrier film 5 described above except that the inorganic barrier layer was formed by the following method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 8.

(Formation of inorganic barrier layer: PHPS coating method)
A dibutyl ether solution containing 20% perhydropolysilazane (PHPS, manufactured by AZ Electronic Materials, NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane) (TMDAH)) and a 20% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) in a ratio of 4: 1 (mass ratio), and further adjusting the dry film thickness Therefore, a coating solution was prepared by diluting with dibutyl ether to a solid content concentration of 5%.

Then, after apply | coating the coating liquid prepared above with the bar coater to the exposed surface by the side of the base layer of the laminated | multilayer film of a base material and a base layer, it dried for 2 minutes at 80 degreeC as drying conditions. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp having a wavelength of 172 nm under the conditions of an oxygen concentration of 0.1% by volume and an irradiation energy of 3.0 J / cm ² to obtain a film thickness of 150 nm. An inorganic barrier layer (composition SiON) was formed.

[Preparation of gas barrier film 9]
A gas barrier film 9 was produced by the same method as the production of the gas barrier film 5 described above except that the inorganic barrier layer was formed by the following method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 9.

(Formation of inorganic barrier layer: vacuum plasma CVD method)
A roll-to-roll type in which two apparatuses each having a film forming unit composed of opposing film forming rolls described in Japanese Patent No. 4268195 are connected (having a first film forming unit and a second film forming unit) An inorganic barrier layer was formed using a vacuum CVD film forming apparatus. The film forming conditions are as follows: the transport speed is 7 m / min, the supply amount of source gas (HMDSO) is 150 cc / min, the supply amount of oxygen gas is 150 cc / min, the degree of vacuum is 1.5 Pa, the applied power is 4.5 kW, and the inorganic film has a thickness of 150 nm. A barrier layer (composition SiOC) was formed.

[Production of Gas Barrier Film 10]
The gas barrier film 10 was produced by the same method as the production of the gas barrier film 5 described above, except that the exposed surface of the inorganic barrier layer was subjected to the following corona treatment instead of the oxygen plasma treatment. . In addition, it confirmed that the acryloyl group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 10 like the above.

(Surface hydrophilization treatment: Corona treatment)
Using a corona treatment device (manufactured by Kasuga Denki Co., Ltd.), surface modification treatment of the exposed surface of the inorganic barrier layer (corona treatment) under the conditions of an output of 300 W, an electrode length of 240 mm, a work electrode distance of 3.0 mm, and a conveying speed of 4 m / min. )

[Preparation of gas barrier film 11]
The gas barrier film 11 was produced by the same method as the production of the gas barrier film 5 described above, except that the following excimer treatment was performed instead of the oxygen plasma treatment as the hydrophilic treatment of the exposed surface of the inorganic barrier layer. . In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 11.

(Surface hydrophilization treatment: excimer treatment)
Using an Xe excimer lamp with a wavelength of 172 nm, the surface modification treatment (excimer treatment) of the exposed surface of the inorganic barrier layer was performed under conditions of an oxygen concentration of 0.1 vol% and an irradiation energy of 1.0 J / cm ² .

[Preparation of gas barrier film 12]
The gas barrier film 12 is produced by the same method as the production of the gas barrier film 5 described above, except that the exposed surface of the inorganic barrier layer is subjected to the following UV ozone treatment instead of the oxygen plasma treatment. did. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 12.

(Surface hydrophilization treatment: UV ozone treatment)
Using a low-pressure mercury lamp, ultraviolet rays (major wavelength 254 nm) were irradiated at 80 ° C. for 10 minutes under atmospheric conditions.

[Preparation of gas barrier film 13]
The gas barrier properties described above, except that the coating amount of the coating liquid when forming the adhesive layer and the solid content concentration at the time of coating are changed so that the dry film thickness of the adhesive layer is 200 nm (value observed by TEM). A gas barrier film 13 was produced by the same method as the production of the film 2.

[Preparation of gas barrier film 14]
The gas barrier properties described above, except that the coating amount of the coating liquid when forming the adhesive layer and the solid content concentration at the time of coating are changed so that the dry film thickness of the adhesive layer is 100 nm (value observed by TEM). A gas barrier film 14 was produced in the same manner as the production of the film 2.

[Preparation of gas barrier film 15]
A gas barrier film 15 was produced by the same method as the production of the gas barrier film 1 described above, except that the adhesive layer was not formed.

[Preparation of gas barrier film 16]
A gas barrier film 16 was produced in the same manner as the production of the gas barrier film 5 described above, except that the exposed surface of the inorganic barrier layer was not subjected to hydrophilic treatment before forming the adhesive layer. It was confirmed in the same manner as above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 16.

[Preparation of gas barrier film 17]
In the formation of the adhesive layer, the gas barrier film 4 described above except that KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) which is an isocyanate group-containing silane coupling agent is used instead of KR-513 which is an organic-inorganic hybrid material. A gas barrier film 17 was produced in the same manner as in the above. In addition, it confirmed that the isocyanate group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 17 similarly to the above. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

[Preparation of gas barrier film 18]
A gas barrier film 18 was produced by the same method as the production of the gas barrier film 5 described above except that the inorganic barrier layer was formed by the following method. It was confirmed in the same manner as above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 18.

(Formation of inorganic barrier layer: sputtering method (composition AlO))
An inorganic barrier layer (composition AlO) having a film thickness of 150 nm was formed in the same manner as in the preparation of the gas barrier film 1 described above except that Al was used as a sputtering target when forming the inorganic barrier layer.

[Preparation of gas barrier film 19]
In the formation of the adhesive layer, the gas barrier film 4 described above except that KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) which is an epoxy group-containing silane coupling agent is used instead of KR-513 which is an organic-inorganic hybrid material. A gas barrier film 19 was produced by the same method as in the above. It was confirmed in the same manner as above that the epoxy group was exposed on the exposed surface of the adhesive layer of the gas barrier film 19. On the other hand, the film thickness of the adhesive layer could not be measured by TEM (that is, it was confirmed that the film thickness of the adhesive layer was 20 nm or less).

<< Production of optical film >>
[Preparation of optical films 1 to 18]
Resin A was prepared by adding 3% of a polymerization initiator (BASF Japan, Irgacure (registered trademark) 184) to pentaerythritol diacrylate, which is a polyfunctional acrylate compound, with respect to 100% of the resin amount.

  On the other hand, semiconductor nanoparticles (CdSe / ZnS) emitting red and green light were respectively synthesized according to the method described in JP-T-2013-505347. The semiconductor nanoparticles were dispersed in a toluene solvent so that the red component and the green component were 0.75 mg and 4.12 mg, respectively. The resin A prepared above was added to this dispersion to prepare a coating solution for forming an acrylic resin-containing light emitting layer in which the content of semiconductor nanoparticles was 1% (solid content).

The acrylic resin-containing light emitting layer forming coating solution prepared above was applied on each of the adhesive layers of the gas barrier films 1 to 18 prepared above to form a quantum dot-containing coating film. Next, the gas barrier film is disposed so that the adhesive layer side of the same gas barrier film is in contact with the quantum dot-containing coating film (two gas barrier films are sandwiched between the quantum dot-containing coating films), and the conditions are 800 mW / cm ² and 300 mJ / cm ² . The optical film 1-18 which has an acrylic resin containing light emitting layer corresponding to each of the gas barrier films 1-18 was produced by curing the quantum dot-containing coating film by applying an ultraviolet irradiation treatment with a high pressure mercury lamp. In addition, the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.

[Preparation of optical film 19]
The optical film 1 described above, except that EPOTECH (registered trademark) OG-142 (manufactured by EPOTECH) was used instead of pentaerythritol diacrylate and Irgacure (registered trademark) 819 (manufactured by BASF Japan) was used as the polymerization initiator. In the same manner as in Preparations 18 to 18, a coating solution for forming an epoxy resin-containing light emitting layer in which the content of semiconductor nanoparticles was 1% (vs. solid content) was prepared.

The coating solution for forming an epoxy resin-containing light emitting layer prepared above was applied on the adhesive layer of the gas barrier film 19 prepared above to form a quantum dot-containing coating film. Next, the adhesive layer side of the same gas barrier film is placed in contact with the quantum dot-containing coating film (two gas barrier films are sandwiched between the quantum dot-containing coating films), and the conditions are 800 mW / cm ² and 1200 mJ / cm ² . The optical film 19 having an epoxy resin-containing light emitting layer corresponding to the gas barrier film 19 was produced by curing the quantum dot-containing coating film by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp. In addition, the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.

[Preparation of optical film 20]
Except for using Crossmer U (manufactured by Nippon Carbide Industries Co., Ltd.), which is a UV cation curable vinyl ether resin, instead of pentaerythritol diacrylate, and using Irgacure (registered trademark) 250 (manufactured by BASF Japan) as a polymerization initiator. In the same manner as in the production of the optical films 1 to 18, a polyvinyl ether resin-containing coating solution for forming a light-emitting layer in which the content of semiconductor nanoparticles was 1% (based on solid content) was prepared.

The polyvinyl ether resin-containing light emitting layer forming coating solution prepared above was applied onto the adhesive layer of the gas barrier film 5 prepared above to form a quantum dot-containing coating film. Next, the gas barrier film is disposed so that the adhesive layer side of the same gas barrier film is in contact with the quantum dot-containing coating film (two gas barrier films are sandwiched between the quantum dot-containing coating films), and the conditions are 800 mW / cm ² and 300 mJ / cm ² . The optical film 20 having a polyvinyl ether resin-containing light-emitting layer corresponding to the gas barrier film 5 was produced by curing the quantum dot-containing coating film by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp. In addition, the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.

<< Measurement of peel strength in optical film >>
About the optical films 1-20 produced above, the peeling strength between the inorganic barrier layer and the light emitting layer in each sample immediately after production was measured. The sample was cut into a size of 1 inch in length and 20 cm in width, and the peel strength in the vertical direction was measured using a peel tester FGPX-0.5 manufactured by SHIMPO. The results are shown in Table 1 below.

<< Measurement of peel strength in optical film >>
(Evaluation of barrier properties)
About the optical film produced above, the luminance was measured immediately after production. In addition, the luminance was measured in the same manner after the same optical film was allowed to stand for 1000 hours under high temperature and high humidity conditions (60 ° C. and 90% RH). Then, the luminance reduction ratio after standing under high temperature and high humidity conditions when the luminance before standing under high temperature and high humidity conditions is taken as 100% is calculated, and a five-step evaluation is performed based on the following criteria. It was. The measurement of the luminance, position the evaluation sample B on a blue LED with an emission wavelength of 450 nm, the brightness with high spectral radiance meter was fixed at 10cm a of CS-2000 (manufactured by Konica Minolta Co., Ltd.) ^{(L *)} This was done by measuring. The results are shown in Table 1 below:
1: Decrease in luminance is 30% or more;
2: The rate of decrease in luminance is 20% or more and less than 30%;
3: The rate of decrease in luminance is 10% or more and less than 20%;
4: The luminance reduction ratio is 5% or more and less than 10%;
5: The luminance reduction rate is less than 5%.

  From the results in Table 1, the optical film (No. 1-12, 16-20) using the gas barrier film (No. 1-12, 16-19) according to the present invention has an adhesive layer thickness of 30 nm. Compared with the optical film using the gas barrier film (No. 13 to 15) which does not have such a configuration by the following and the peel strength between the inorganic barrier layer and the light emitting layer is 2 N / 20 mm or more. It turns out that the fall of the brightness | luminance of an optical film when an optical film is put on high-temperature, high-humidity conditions can be suppressed.

  This application is based on Japanese Patent Application No. 2015-043015 filed on Mar. 4, 2015, the disclosure of which is incorporated by reference in its entirety.

1 optical film,
11 Gas barrier film,
12 substrate,
13 Inorganic barrier layer,
14 Adhesive layer,
20 Light emitting layer.

Claims (11)

A light emitting layer comprising semiconductor nanoparticles and an ultraviolet curable resin;
A base material, an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material, and an adhesive layer disposed on the surface of the inorganic barrier layer opposite to the base material. A pair of gas barrier films sandwiching the light emitting layer so that the adhesive layer is in contact with the light emitting layer;
Have
The film thickness of the adhesive layer (measured with a transmission electron microscope) is 30 nm or less, and the peel strength between the inorganic barrier layer and the light emitting layer (with a peel tester FGPX-0.5 manufactured by SHIMPO) An optical film whose measurement is 2 N / 20 mm or more.   The optical film according to claim 1, wherein the adhesive layer is formed such that the inorganic compound and the ultraviolet curable resin are bonded through a chemical bond.   The chemical bond is derived from a compound having a reactive group capable of forming a bond with the inorganic compound and a reactive group capable of forming a bond with the raw material of the ultraviolet curable resin in one molecule. The optical film according to claim 1 or 2.   The compound is a silane coupling agent containing an alkoxysilyl group and one or more functional groups selected from the group consisting of a (meth) acryloyl group, a vinyl group, and an epoxy group. 3. The optical film as described in 3.   The optical film according to claim 3 or 4, wherein the ultraviolet curable resin is an acrylic resin and the compound is an acryloyl group-containing silane coupling agent.   The optical film according to claim 1, wherein the ultraviolet curable resin is an acrylic resin or an epoxy resin.   The optical film according to any one of claims 1 to 6, wherein the inorganic oxide is a silicon compound having a composition of SiO, SiON, or SiOC. A base material, an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material, and an adhesive layer disposed on the surface of the inorganic barrier layer opposite to the base material. A laminate manufacturing step of manufacturing a laminate by sandwiching a light emitting layer precursor containing semiconductor nanoparticles and an ultraviolet curable resin by a pair of gas barrier films having,
An ultraviolet irradiation step of irradiating the laminate with ultraviolet rays to cure the ultraviolet curable resin to form an ultraviolet curable resin;
Including
The manufacturing method of an optical film which performs the said laminated body preparation process so that the said contact bonding layer and the said light emitting layer precursor may contact | connect.   The manufacturing method of the optical film of Claim 8 whose said contact bonding layer is a layer which has an acryloyl group containing silane coupling agent as a main component.   The optical film production according to claim 8 or 9, further comprising a hydrophilization treatment step in which a contact angle with respect to water of the exposed surface is set to 20 ° or less before providing the adhesive layer on the exposed surface of the inorganic barrier layer. Method.   An optical device comprising the optical film according to any one of claims 1 to 7 or the optical film produced by the production method according to any one of claims 8 to 10.