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WO2016140340A1 - Film optique, et dispositif optique l'utilisant - Google Patents

Film optique, et dispositif optique l'utilisant Download PDF

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Publication number
WO2016140340A1
WO2016140340A1 PCT/JP2016/056737 JP2016056737W WO2016140340A1 WO 2016140340 A1 WO2016140340 A1 WO 2016140340A1 JP 2016056737 W JP2016056737 W JP 2016056737W WO 2016140340 A1 WO2016140340 A1 WO 2016140340A1
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Prior art keywords
layer
inorganic
group
film
meth
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Japanese (ja)
Inventor
千代子 竹村
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Konica Minolta Inc
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Konica Minolta Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means

Definitions

  • the present invention relates to an optical film and an optical device using the same.
  • semiconductor nanoparticles also referred to as “Quantum Dot (QD)”
  • QD Quantum Dot
  • 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.
  • JP 2013-544018 A and International Publication No. 2014/113562 disclose 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.
  • QD quantum dots
  • 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 formed on the inorganic oxide thin film.
  • a technique for forming a transparent barrier film by providing a film is disclosed.
  • 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.
  • 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.
  • Japanese Patent Laid-Open No. 10-156998 by providing a thin film made of a silane coupling agent, adhesion between an inorganic oxide thin film (inorganic barrier layer) and a 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.
  • QD quantum dots
  • 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.
  • QD quantum dots
  • the present inventor has conducted intensive research 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the thickness of the adhesive layer 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 2 N / 20 mm or more (measured with a peeling tester FGPX-0.5 manufactured by company).
  • 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.
  • 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.
  • 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.
  • the layer structure of the optical film according to one embodiment of the present invention will be described with reference to FIG.
  • an optical film 1 has a configuration in which a light emitting layer 20 is sandwiched between a pair of gas barrier films 11.
  • 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.
  • 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.
  • 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.
  • a resin substrate plastic film or sheet
  • a film or sheet 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.
  • 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
  • a heat-resistant transparent film product name: Sila-DEC, manufactured by Chisso Corporation having a silsesquioxane having a basic skeleton, and a resin film formed by laminating two or more layers of the above resin It can gel.
  • the thickness of the substrate is not particularly limited, but is preferably 5 to 300 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • the substrate may have a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer.
  • a functional layer such as a transparent conductive layer, a primer layer, or a clear hard coat layer.
  • 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 used.
  • the base material according to the present invention is preferably 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.
  • 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.
  • 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.
  • the inorganic barrier layer In the gas barrier film according to the present invention, at least one inorganic barrier layer is formed on a substrate.
  • 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.
  • the inorganic compound is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides.
  • 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).
  • the inorganic barrier layer has high density and further has gas barrier properties.
  • 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).
  • PVD method physical vapor deposition
  • CVD chemical vapor deposition
  • CVD chemical vapor deposition
  • the physical vapor deposition 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.
  • a target material for example, a thin film such as a carbon film
  • 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.
  • 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 method (Chemical Vapor Deposition, CVD method) is a method of depositing a film by supplying a source gas containing a target thin film component onto a substrate and performing a chemical reaction on the surface of the substrate or in the gas phase. 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.
  • 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 can be appropriately employed.
  • the inorganic barrier layer formed by such a method is preferably a layer containing an oxide, nitride, oxynitride or oxycarbide.
  • 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.
  • a coating film formed by applying a liquid containing an inorganic compound preferably a liquid containing a silicon compound
  • the silicon compound will be described as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.
  • the silicon compound is not particularly limited as long as a coating solution containing a silicon compound can be prepared.
  • a coating solution containing a silicon compound can be prepared.
  • polysilazane compounds, silazane compounds, aminosilane compounds, silylacetamide compounds, silylimidazole compounds, and other silicon compounds containing nitrogen are used.
  • the polysilazane compound is a polymer having a silicon-nitrogen bond.
  • polysilazane compound is also abbreviated as “polysilazane”.
  • Examples of 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.
  • the polysilazane compound is commercially available in a solution in an organic solvent.
  • examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310 manufactured by AZ Electronic Materials Co., Ltd. NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and the like.
  • Glycidol-added polysilazane 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 obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), and metal fine particles.
  • Addition of fine metal particles Rishirazan JP 7-196986, such as, include polysilazane compounds ceramic at low temperatures.
  • silazane compound examples 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 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.
  • silylacetamide compound examples 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 include 1- (tert-butyldimethylsilyl) imidazole, 1- (dimethylethylsilyl) imidazole, 1- (dimethylisopropylsilyl) imidazole, and N-trimethylsilylimidazole. However, it is not limited to these.
  • 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.
  • 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.
  • the content of polysilazane in the inorganic barrier layer before the modification treatment may be 100% by mass when the total mass of the inorganic barrier layer is 100% by mass.
  • 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.
  • 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.
  • the gas barrier film as a whole has a gas barrier property (water vapor) A process for forming an inorganic thin film at a level that can contribute to the development of a transmittance of 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ day or less).
  • 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.
  • 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.
  • a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.
  • 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.
  • 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.
  • nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
  • 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.
  • a layer is formed using a sol-gel method
  • 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.
  • 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
  • a heating element such as a heat block
  • an external heater such as a resistance wire
  • an infrared region such as an IR heater
  • the temperature of the coating film during the heat treatment is preferably adjusted appropriately in the range of 50 to 250 ° C, and more preferably in the range of 50 to 120 ° C.
  • the heating time is preferably in the range of 1 second to 10 hours, 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.
  • 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.
  • 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.
  • the irradiation intensity and the irradiation time are set within a range where the substrate carrying the irradiated inorganic barrier layer is not damaged.
  • a 2 kW (80 W / cm ⁇ 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm 2 , preferably 50 to 200 mW / cm.
  • the distance between the base material and the ultraviolet irradiation lamp is set so as to be 2, and irradiation can be performed for 0.1 seconds to 10 minutes.
  • the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more
  • the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength.
  • a modification treatment at a higher temperature is possible.
  • the substrate temperature at the time of ultraviolet irradiation 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.
  • ultraviolet ray generating means examples 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.
  • 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.
  • UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.
  • 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.
  • an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.
  • 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.
  • 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 used and the inorganic barrier layer.
  • the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment).
  • the treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds 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.
  • the radiation source in the present invention may be any radiation source that emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm.
  • Excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp)
  • 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.
  • 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.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power.
  • 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.
  • 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 perform in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays 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.
  • the gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas 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.
  • the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm 2 to 10 W / cm 2 , more preferably 30 mW / cm 2 to 200 mW / 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 it preferably from 10 ⁇ 10000mJ / 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.
  • the vacuum ultraviolet light used for reforming may be generated by plasma formed in a gas containing at least one of CO 2 and CH 4.
  • 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.
  • the film density of the inorganic barrier layer can be appropriately set according to the purpose.
  • 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.
  • each inorganic barrier layer may have the same composition or a different composition.
  • 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.
  • a combination of a layer formed by a vacuum film forming method and a layer formed by a coating method may be used.
  • 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 for forming a metal atom-containing layer described later.
  • a nitrogen element or a carbon element from the viewpoints of stress relaxation and absorption of ultraviolet rays used for forming a metal atom-containing layer described later.
  • 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 of 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.
  • an adhesive layer 14 is disposed on the surface (exposed surface) of the inorganic barrier layer 13 opposite to the substrate 12.
  • 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.
  • TEM transmission electron microscope
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • a functional group such as a (meth) acryloyl group
  • the acryloyl group is an acyl group derived from acrylic acid represented by “CH 2 ⁇ CH—C ( ⁇ O) —”
  • the methacryloyl group is “CH 2 ⁇ C (CH 3 ) —C ( ⁇ O) — ”is an acyl group derived from methacrylic acid
  • “ (meth) acryloyl group ” is a collective name.
  • 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.
  • 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.
  • 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.
  • a value measured by a technique described in Examples described later using a peel tester FGPX-0.5 manufactured by SHIMPO is adopted.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 )
  • a compound containing a (meth) acryloyl group and an alkoxysilyl group in one molecule metal .
  • an alkoxysilyl moiety contained in the compound can form a siloxane bond with the silicon atom.
  • the (meth) acryloyl group contained in the compound forms a chemical bond with the silicon atom contained in the inorganic compound via another atom.
  • 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.
  • 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 oligomers 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.
  • “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.
  • 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.
  • 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.
  • 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.
  • a mode in which the adhesive layer is composed of two or more layers (preferably two layers) is exemplified.
  • 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.
  • 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”)
  • An example is a method in which the dissolved solution is applied to the surface of the inorganic barrier layer 13 and dried.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the surface of the inorganic barrier layer is hydrophilized.
  • the inorganic compound constituting the inorganic barrier layer contains silicon atoms, a large number of silanol groups (—Si—OH groups) are formed. It forms on the surface of the inorganic barrier layer.
  • 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.
  • the number (density) of functional groups such as (meth) acryloyl groups exposed on the surface of the inorganic barrier layer can be increased.
  • the adhesion at the interface between these two layers can be further improved.
  • 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. For example, 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 the like
  • polyester polyols such as succinate and polycaprolactone, and ⁇ , ⁇ -poly (1,6-hexylene carbonate) diol, ⁇ , ⁇ -poly (3-methyl-1,5- Styrene carbonate) diol, ⁇ , ⁇ -poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, ⁇ , ⁇ -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.
  • an epoxy resin There is no restriction
  • 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 polyol and polyisocyanate with hydroxyl group-containing (meth) acrylate, or polyol and isocyanato group-containing (meth) acrylate.
  • 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.
  • polyisocyanate examples 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.
  • 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-mentioned (meth) acryloyl group-containing compound.
  • (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, etc.
  • a cyclic ether group such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth
  • Monofunctional (meth) acryloyl group-containing compounds having an aromatic group lauryl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobutyl (meth) acrylate
  • Monofunctional (meth) acryloyl group-containing compounds having a chain aliphatic group such as acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, isoamyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) )
  • Monofunctional (meth) acryloyl group-containing compound having an aromatic ring such as acrylate, polyethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, nonanediol di (meth) acrylate, hexanediol
  • 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.
  • 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.
  • 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.
  • photopolymerization initiator examples 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, -Isopropylthiox
  • the said solution may contain a filler for the purpose of slipperiness and winding-up property.
  • 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.
  • silica-based inorganic fillers are particularly preferable.
  • the shape of the filler is preferably spherical, and the particle size is preferably in the range of 10 to 50 ⁇ m.
  • 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.
  • 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.
  • other members are not particularly limited, and members used for conventional gas barrier films can be used in the same manner 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.
  • the other member may exist as a single layer or may have a laminated structure of two or more layers.
  • 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.
  • 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.
  • UV curable organic / inorganic hybrid hard coating material manufactured by JSR Corporation OPSTAR (registered trademark) series (polymerizable unsaturated group on silica fine particles) And a compound obtained by bonding an organic compound having a compound (a).
  • 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 resistance epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nittobo Co., Ltd.
  • thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydride Resins.
  • 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 ⁇ m many times.
  • AFM Anamic Force Microscope
  • the thickness of the underlayer is not particularly limited, but is preferably in the range of 0.1 to 10 ⁇ m.
  • an anchor coat 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).
  • 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., “X-12-2400” 3% isopropyl alcohol solution) can be used.
  • the thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 ⁇ m.
  • 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 ⁇ m, preferably 2 to 7 ⁇ m.
  • 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” refers 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.
  • the band gap of the semiconductor nanoparticles increases in proportion to “R ⁇ 2 ” (so-called quantum confinement effect).
  • 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.
  • such luminescent semiconductor nanoparticles are used as a luminescent material of the luminescent layer.
  • the content of the semiconductor nanoparticles contained in the light emitting layer is preferably 0.01 to 50% by weight, more preferably 0.5 to 30% by weight, and more preferably 2.0% by weight based on the total weight 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 the average particle diameter corresponding to the target emission color.
  • the average particle diameter of the semiconductor nanoparticles is preferably 3.0 to 20 nm, and when green light emission is desired, it is preferably 1.5 to 10 nm.
  • the thickness is preferably 1.0 to 3.0 nm.
  • 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.
  • 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.
  • 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.
  • the average particle diameter of the semiconductor nanoparticle in this specification shall mean the average value of the particle diameter of 300 particle
  • 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.
  • 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).
  • Constituent material 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 (
  • 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)
  • ZincO zinc oxide
  • ZnS zinc sulfide
  • ZnSe zinc selenide
  • ZnTe zinc telluride
  • CdO cadmium oxide
  • CdS cadmium sulfide
  • CdSe cadmium selenide
  • CdTe cadmium telluride
  • HgS mercury sulfide
  • HgSe mercury selenide
  • HgTe mercury telluride
  • 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 io
  • 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
  • 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
  • ZnO, ZnS, ZnSe, ZnTe CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe and other II-VI group compound semiconductors
  • 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 trace amounts of various elements as impurities as necessary. By adding such a doping substance, the emission characteristics can be greatly improved.
  • the band gap refers to the energy difference between the valence band of the semiconductor nanoparticles and the conductor.
  • the band gap (eV) of the semiconductor nanoparticles can be obtained using a Tauc plot.
  • Tauc plot which is one of the optical scientific measurement methods of the band gap (eV), will be described.
  • 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 a coating layer composed of an inorganic coating layer or 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.
  • a gradient structure composed of two or more kinds of compounds.
  • 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.
  • the thickness of the shell region is not particularly limited, but is preferably 0.1 to 10 nm, and more preferably 0.1 to 5 nm.
  • the emission color of semiconductor nanoparticles can be controlled by the average particle diameter.
  • 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.
  • 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.
  • 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.
  • the surface modifier examples 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, trioctylphosphineoxy 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; Aminoalkanes such as octylamine, decylamine, dodecyl
  • 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.
  • trialkylphosphines, organic phosphorus compounds, aminoalkanes, tertiary amines, organic nitrogen compounds, dialkyl sulfides, dialkyl sulfoxides, organic sulfur compounds, higher fatty acids, and alcohols are preferable.
  • 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.
  • an aqueous raw material is used, for example, an alkane 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.
  • 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.
  • ultraviolet curable resins examples include urethane (meth) acrylate resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, acrylic resins such as polyol (meth) acrylate resins, or epoxy resins.
  • 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).
  • an epoxy (meth) acrylate resin for example, Unidic (registered trademark) V-5500 ( DIC Corporation)
  • urethane (meth) acrylate resins are preferably used.
  • 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” is preferably an epoxy group.
  • 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” 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.
  • the photopolymerization initiator of the ultraviolet curable resin the above-described materials can be similarly used as the constituent material of the adhesive layer.
  • the thickness of the quantum dot layer (light emitting layer) according to this embodiment is not particularly limited, but is preferably 10 to 500 ⁇ m, and more preferably 30 to 300 ⁇ m.
  • the thickness of the quantum dot layer (light emitting layer) is 10 ⁇ m or more, it is easy to adjust the light emission balance of B, G, and R, and good color gamut reproducibility can be obtained.
  • the thickness of the quantum dot layer (light emitting layer) is 500 ⁇ m or less, the quantum dot layer (light emitting layer) can be efficiently cured, and good productivity can be obtained.
  • 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
  • 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.
  • the obtained laminate is subjected to ultraviolet irradiation treatment.
  • 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).
  • LCD liquid crystal display
  • 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.
  • 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 ⁇ m.
  • drying was performed at 80 ° C. for 2 minutes as drying conditions.
  • 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.
  • PGME propylene glycol monomethyl ether
  • 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.
  • 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.
  • 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.
  • the measurement conditions of TEM for measuring the dry film thickness of an adhesive layer are as follows.
  • 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.
  • 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.
  • 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).
  • gas barrier film 5 In the formation of the adhesive layer, the gas barrier film 4 described above was used 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.
  • KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • KR-513 which is an organic-inorganic hybrid material.
  • a gas barrier film 5 was produced in the same manner as in the above.
  • 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).
  • gas barrier film 6 In the formation of the adhesive layer, the gas barrier film 4 described above was used except that KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a methacryloyl group-containing silane coupling agent, was used instead of KR-513, which was an organic-inorganic hybrid material.
  • KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.
  • KR-513 which was an organic-inorganic hybrid material.
  • a gas barrier film 6 was produced in the same manner as in the above.
  • the methacryloyl group was exposed on the exposed surface of the contact bonding layer of the gas-barrier film 6 similarly to the above.
  • 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).
  • 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.
  • the coating liquid prepared above with the bar coater to the exposed surface by the side of the base layer of the laminated
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • gas barrier film 17 In the formation of the adhesive layer, the gas barrier film 4 described above except that KBE-9007 (made by Shin-Etsu Chemical Co., Ltd.), an isocyanate group-containing silane coupling agent, was 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).
  • 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.
  • composition AlO sputtering method
  • 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.
  • KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.
  • 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).
  • 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.
  • a polymerization initiator BASF Japan, Irgacure (registered trademark) 184
  • pentaerythritol diacrylate which is a polyfunctional acrylate compound
  • semiconductor nanoparticles (CdSe / ZnS) emitting red and green light were respectively synthesized.
  • 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 onto each of the adhesive layers of the gas barrier films 1 to 18 prepared above to form quantum dot-containing coating films.
  • 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 to 18 having an acrylic resin-containing light-emitting layer corresponding to each of the gas barrier films 1 to 18 was prepared by curing the quantum dot-containing coating film by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp.
  • the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.
  • 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.
  • EPOTECH registered trademark
  • Irgacure registered trademark 819
  • 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.
  • 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.
  • the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.
  • 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.
  • 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.
  • the film thickness of the hardened layer (light emitting layer) of the quantum dot containing coating film was 100 micrometers.
  • 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.
  • 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

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Abstract

L'invention vise à fournir un moyen dans un film optique obtenu en commandant la mise en sandwich d'une couche d'émission de lumière comprenant des points quantiques (QD) entre deux couches barrière contre les gaz ayant individuellement une couche barrière inorganique comprenant un composé inorganique placé sur un matériau de base. Ledit moyen réduit au maximum la diminution dans le temps des propriétés des couches barrière contre les gaz et la cohésion entre la couche barrière inorganique et la couche d'émission de lumière (en particulier dans des conditions de haute-température et de forte humidité). L'invention propose ainsi une couche d'émission de lumière contenant des nanoparticules semi-conductrices et une résine durcissable aux UV ; et une paire de couches barrière contre les gaz. Chacune des couches barrière comprend un matériau de base, une couche barrière inorganique comprenant un composé inorganique placé sur au moins une surface du matériau de base, et une couche adhésive placée sur la surface du côté de la couche barrière inorganique opposée au matériau de base. Chacune des couches barrière prend en sandwich la couche d'émission de lumière de telle sorte que les couches adhésives viennent en contact avec la couche d'émission de lumière. L'épaisseur des couches adhésives (mesurée à l'aide d'un microscope électronique à transmission) est égale ou inférieure à 30 nm, et la résistance au pelage entre les couches barrière inorganiques et la couche d'émission de lumière (mesurée avec un testeur de pelage FGPX-0.5 (SHIMPO)) est égale ou supérieure à 2N/20 mm.
PCT/JP2016/056737 2015-03-04 2016-03-04 Film optique, et dispositif optique l'utilisant Ceased WO2016140340A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033665A1 (fr) * 2015-08-21 2017-03-02 コニカミノルタ株式会社 Film barrière contre les gaz, son procédé de fabrication et film optique
WO2017086319A1 (fr) * 2015-11-18 2017-05-26 凸版印刷株式会社 Film protecteur et feuille de conversion de longueur d'onde
WO2018046963A1 (fr) * 2016-09-12 2018-03-15 Nanoco Technologies Ltd Revêtement barrière contre les gaz pour nanoparticules semi-conductrices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020113638A (ja) * 2019-01-11 2020-07-27 株式会社ジャパンディスプレイ エレクトロルミネセンス表示装置及びエレクトロルミネセンス表示装置の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130043677A (ko) * 2010-07-30 2013-04-30 이 아이 듀폰 디 네모아 앤드 캄파니 플루오르화된 공중합체 수지 층 및 봉지제 층을 함유하는 다층 필름
JP2014058154A (ja) * 2012-08-23 2014-04-03 Toppan Printing Co Ltd ガスバリア性フィルム及び太陽電池モジュール用保護シート
JP2014512668A (ja) * 2011-02-18 2014-05-22 スリーエム イノベイティブ プロパティズ カンパニー 接着テープ及び太陽電池組立体、並びにそれらから作成される物品
WO2015022882A1 (fr) * 2013-08-12 2015-02-19 富士フイルム株式会社 Film optique, film barrière, élément de conversion de lumière, unité de rétroéclairage et dispositif d'affichage à cristaux liquides
WO2015041316A1 (fr) * 2013-09-20 2015-03-26 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides et élément de conversion de lumière
JP2015065158A (ja) * 2013-08-26 2015-04-09 富士フイルム株式会社 光変換部材、バックライトユニット、および液晶表示装置、ならびに光変換部材の製造方法
WO2016010116A1 (fr) * 2014-07-18 2016-01-21 凸版印刷株式会社 Film de protection pour feuille de conversion de longueur d'onde, feuille de conversion de longueur d'onde et unité de rétroéclairage
WO2016052624A1 (fr) * 2014-09-30 2016-04-07 富士フイルム株式会社 Procédé de production pour élément de conversion de longueur d'onde, élément de conversion de longueur d'onde, unité de rétroéclairage, et dispositif d'affichage à cristaux liquides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014199977A (ja) * 2013-03-29 2014-10-23 旭化成エレクトロニクス株式会社 増幅回路及びデバイス

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130043677A (ko) * 2010-07-30 2013-04-30 이 아이 듀폰 디 네모아 앤드 캄파니 플루오르화된 공중합체 수지 층 및 봉지제 층을 함유하는 다층 필름
JP2014512668A (ja) * 2011-02-18 2014-05-22 スリーエム イノベイティブ プロパティズ カンパニー 接着テープ及び太陽電池組立体、並びにそれらから作成される物品
JP2014058154A (ja) * 2012-08-23 2014-04-03 Toppan Printing Co Ltd ガスバリア性フィルム及び太陽電池モジュール用保護シート
WO2015022882A1 (fr) * 2013-08-12 2015-02-19 富士フイルム株式会社 Film optique, film barrière, élément de conversion de lumière, unité de rétroéclairage et dispositif d'affichage à cristaux liquides
JP2015065158A (ja) * 2013-08-26 2015-04-09 富士フイルム株式会社 光変換部材、バックライトユニット、および液晶表示装置、ならびに光変換部材の製造方法
WO2015041316A1 (fr) * 2013-09-20 2015-03-26 富士フイルム株式会社 Dispositif d'affichage à cristaux liquides et élément de conversion de lumière
WO2016010116A1 (fr) * 2014-07-18 2016-01-21 凸版印刷株式会社 Film de protection pour feuille de conversion de longueur d'onde, feuille de conversion de longueur d'onde et unité de rétroéclairage
WO2016052624A1 (fr) * 2014-09-30 2016-04-07 富士フイルム株式会社 Procédé de production pour élément de conversion de longueur d'onde, élément de conversion de longueur d'onde, unité de rétroéclairage, et dispositif d'affichage à cristaux liquides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017033665A1 (fr) * 2015-08-21 2017-03-02 コニカミノルタ株式会社 Film barrière contre les gaz, son procédé de fabrication et film optique
WO2017086319A1 (fr) * 2015-11-18 2017-05-26 凸版印刷株式会社 Film protecteur et feuille de conversion de longueur d'onde
WO2018046963A1 (fr) * 2016-09-12 2018-03-15 Nanoco Technologies Ltd Revêtement barrière contre les gaz pour nanoparticules semi-conductrices
CN109804041A (zh) * 2016-09-12 2019-05-24 纳米技术有限公司 用于半导体纳米颗粒的气体阻挡涂层
JP2019536653A (ja) * 2016-09-12 2019-12-19 ナノコ テクノロジーズ リミテッド 半導体ナノ粒子用のガスバリアコーティング

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