WO2016140339A1 - Procédé de fabrication d'un film barrière contre les gaz - Google Patents

Procédé de fabrication d'un film barrière contre les gaz Download PDF

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Publication number
WO2016140339A1
WO2016140339A1 PCT/JP2016/056736 JP2016056736W WO2016140339A1 WO 2016140339 A1 WO2016140339 A1 WO 2016140339A1 JP 2016056736 W JP2016056736 W JP 2016056736W WO 2016140339 A1 WO2016140339 A1 WO 2016140339A1
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layer
gas barrier
film
barrier layer
meth
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PCT/JP2016/056736
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English (en)
Japanese (ja)
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宏司 高木
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コニカミノルタ株式会社
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Priority to JP2017503726A priority Critical patent/JPWO2016140339A1/ja
Publication of WO2016140339A1 publication Critical patent/WO2016140339A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering

Definitions

  • the present invention relates to a method for producing a gas barrier film.
  • an ultraviolet curable resin layer cured by irradiating an ultraviolet curable resin with ultraviolet rays (UV) may be provided so as to be adjacent to the inorganic barrier layer.
  • An example of such an ultraviolet curable resin layer is a protective layer (hard coat layer) for protecting the surface of the inorganic barrier layer.
  • 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.
  • 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 has conducted various studies on the performance of the laminate in which the ultraviolet curable resin layer as described above is disposed so as to be adjacent to the inorganic barrier layer made of an inorganic compound disposed on the substrate.
  • the inorganic barrier layer of a gas barrier film using a conventionally known inorganic barrier layer is disposed as it is adjacent to the ultraviolet curable resin layer, the inorganic barrier layer and the ultraviolet curable resin layer
  • the adhesion decreases with time. It has also been found that such a problem of lowering adhesiveness is particularly prominent when the laminate is placed under conditions of high temperature and high humidity.
  • the present inventor further sought out means for improving the adhesion between the inorganic barrier layer and the ultraviolet curable resin layer.
  • an attempt was made to bond using a silane coupling agent as disclosed in JP-A-10-156998, but only by applying the technique disclosed in JP-A-10-156998, As a result, it was impossible to prevent a decrease in adhesion.
  • the ultraviolet curable resin layer is a protective layer (hard coat layer)
  • the adhesiveness is not sufficient, the protective effect by the protective layer may be reduced.
  • the ultraviolet curable resin layer is a quantum dot layer
  • the adhesion is not sufficient, the effect of blocking oxygen and moisture by the inorganic barrier layer against the quantum dot layer is reduced, and as a result, the emission luminance from the quantum dot layer May decrease.
  • the present invention has been made in view of the above circumstances, and when the inorganic barrier layer is used so as to be adjacent to the ultraviolet curable resin layer, the inorganic barrier layer and the ultraviolet curable resin layer (In particular, an object is to provide means capable of suppressing the deterioration of adhesion and gas barrier properties over time (under high temperature and high humidity conditions).
  • a silane coupling agent containing a (meth) acryloyl group is a main component on the exposed surface of the inorganic barrier layer of the laminate in which an inorganic barrier layer made of an inorganic compound is disposed on at least one surface of the substrate.
  • the coating solution was applied to form a coating film, and the coating film was dried to produce a gas barrier film, thereby finding that the above problems could be solved, and the present invention was completed.
  • a method for producing a gas barrier film includes a (meth) acryloyl group on the exposed surface of the gas barrier layer of a laminate having a base material and an inorganic barrier layer made of an inorganic compound and disposed on at least one surface of the base material.
  • a step of applying a coating solution containing a silane coupling agent and a solvent to form a coating film (coating layer forming step) and a step of drying the coating film (drying step).
  • content of the said silane coupling agent contained in the said coating liquid has the characteristics in the point which is 95 mass% or more with respect to 100 mass% of the total amount of solid content of the said coating liquid.
  • an exposed surface of the inorganic barrier layer of the laminate having a base material and an inorganic barrier layer made of an inorganic compound disposed on at least one surface of the base material
  • a coating film forming step of forming a coating film by applying a coating solution containing a silane coupling agent containing a (meth) acryloyl group and a solvent, and a drying step of drying the coating film, and included in the coating solution There is provided a method for producing a gas barrier film, wherein the content of the silane coupling agent is 95% by mass or more based on 100% by mass of the total solid content of the coating solution.
  • the inorganic barrier layer when the inorganic barrier layer is disposed and used adjacent to the ultraviolet curable resin layer, the inorganic barrier layer and the ultraviolet curable resin layer It is possible to suppress a decrease in adhesion and gas barrier properties over time (particularly under high temperature and high humidity conditions).
  • acryloyl is formed on the exposed surface of the inorganic barrier layer. The group is considered to be exposed.
  • This acryloyl group forms a chemical bond with the ultraviolet curable resin that constitutes the ultraviolet curable resin layer adjacent to the inorganic barrier layer, resulting in a strong bonding region at the interface, resulting in adhesion between these layers. It is presumed that the improvement of the adhesiveness and gas barrier properties over time is suppressed. In addition, since the thickness of the bonding region is extremely thin, oxygen and moisture can be prevented from entering from the bonding region, which is considered to lead to the suppression of gas barrier properties. In addition, this invention shall not be limitedly interpreted by the said mechanism in any way.
  • a (meth) acryloyl group is formed on the exposed surface of the inorganic barrier layer of the laminate having a base material and an inorganic barrier layer made of an inorganic compound disposed on at least one surface of the base material.
  • a coating solution is formed by applying a coating solution containing a silane coupling agent and a solvent.
  • 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.
  • Inorganic barrier layer In the laminate prepared in this step, at least one inorganic barrier layer is formed on the 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.
  • the laminated body prepared in this process contains the base material and inorganic barrier layer which were mentioned above as an essential component, it may further contain another member.
  • the substrate and the inorganic barrier layer between the inorganic barrier layers (if there are multiple inorganic barrier layers); or on the other side of the substrate where the inorganic barrier layer is not formed You may have a member.
  • 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.
  • an underlayer may be disposed between the base material and the inorganic barrier layer.
  • 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 according to 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 component of the "coating liquid" used in this process is demonstrated.
  • Solvents include, for example, 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; methanol, ethanol, isopropyl alcohol And alcohol solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and diethylene glycol monomethyl ether.
  • silane coupling agent having (meth) acryloyl group examples include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3 -(Meth) acryloyloxypropylmethyldiethoxysilane and the like.
  • Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, and KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.
  • the content of the silane coupling agent contained in the coating solution is 95% by mass or more with respect to 100% by mass of the solid content of the coating solution, preferably It is 98 mass% or more, More preferably, it is 99 mass% or more, More preferably, it is 99.5 mass% or more, Especially preferably, it is 99.8 mass% or more, Most preferably, it is 100 mass%.
  • the surface of the inorganic barrier layer 13 is formed by applying a coating solution in which most of the solid content contained in the coating solution is a (meth) acryloyl group-containing silane coupling agent and drying to form a coating film.
  • a gas barrier film with a (meth) acryloyl group exposed can be produced.
  • the inorganic compound constituting the inorganic barrier layer 13 contains silicon atoms (for example, having a composition such as SiO, SiON, SiOC, etc.)
  • the (meth) acryloyl group-containing silane is produced by the production method according to the present invention.
  • the alkoxysilyl group contained in the silane coupling agent is hydrolyzed with the silicon atoms contained in the inorganic compound as time passes. causes a condensation reaction.
  • the (meth) acryloyl group contained in the said silane coupling agent comes to form a chemical bond with the silicon atom contained in the said inorganic compound through another atom.
  • the solid content of the coating solution may include components other than the silane coupling agent.
  • components other than the silane coupling agent include polyol poly (meth) acrylate, epoxy (meth) acrylate, and urethane. (Meth) acrylate, (meth) acryl monomer, etc. are mentioned.
  • 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
  • a photopolymerization initiator suitable for the coating solution May be added, and the coating solution obtained by applying and drying the above solution may be subjected to light irradiation treatment to polymerize a part of the (meth) acryloyl group-containing compound.
  • a conventionally known polymerization inhibitor may be added for the purpose of preventing unintentional polymerization of the (meth) acryloyl group-containing compound.
  • 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 by irradiation with light such as near infrared rays, visible light, 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 content of the predetermined silane coupling agent contained in the coating liquid is 95% by mass or more with respect to 100% by mass of the solid content of the coating liquid. .
  • the content is at most 5% by mass or less with respect to 100% by mass of the solid content in the coating solution.
  • the photopolymerization initiator is included, the content of the above compound is further reduced. Therefore, in the present invention, even when the above compound is used in combination with the predetermined silane coupling agent, it is preferable that no photopolymerization initiator is contained.
  • a step for hydrophilizing the exposed surface of the inorganic barrier layer before the coating film forming step described above.
  • the degree of hydrophilicity of the exposed surface of the inorganic barrier layer can be determined using the contact angle with water as an index. Specifically, hydrophilization is performed so that the contact angle of water on the exposed surface of the inorganic barrier layer is preferably 20 ° or less, more preferably 18 ° or less, still more preferably 15 ° or less, and particularly preferably 10 ° or less. It is preferable to perform a processing step.
  • hydrophilic treatment examples include oxygen plasma treatment, corona treatment, excimer (vacuum ultraviolet) treatment, UV ozone treatment, and the like.
  • oxygen plasma treatment corona treatment
  • excimer (vacuum ultraviolet) treatment UV ozone treatment
  • the surface of the inorganic barrier layer is hydrophilized.
  • silanol groups —Si—OH groups
  • the silanol group reacts with the alkoxysilyl group contained in the (meth) acryloyl group-containing silane coupling agent, and thus the (meth) acryloyl group exposed on the surface of the inorganic barrier layer.
  • the number (density) can be increased.
  • the ultraviolet curable resin layer is provided so as to be adjacent to the inorganic barrier layer, there is an advantage that the adhesion at the interface between these two layers can be further improved.
  • a step (drying step) of drying the coating film formed in the above-described coating film forming step is performed.
  • the drying conditions are not particularly limited, but the drying temperature is preferably 55 ° C or higher, more preferably 60 ° C or higher. Although there is no restriction
  • the drying time is preferably 40 seconds or longer, more preferably 45 seconds or longer.
  • it is 240 seconds or less, It is more preferable that it is 120 seconds or less, It is 90 seconds or less More preferably, it is particularly preferably 60 seconds or less.
  • the coating film forming step and the drying step are continuously performed on the exposed surface of the inorganic barrier layer of the film unwound from the roll of the laminate of the base material and the inorganic barrier layer. From the viewpoint of producing a gas barrier film with high productivity, it is preferable that the drying conditions in the drying step are relatively high and relatively long.
  • the coating film formed on the exposed surface of the inorganic barrier layer faces when the film that has undergone the drying process is wound on a roll. Then, the risk that the original function will not be exhibited when the back side of the gas barrier film to be wound and the protective film is pasted and this is wound and used next time is reduced.
  • a gas barrier film 11 includes a base material 12 and an inorganic barrier layer 13 disposed on one surface of the base material 12. And the coating film is formed in the surface (exposed surface) on the opposite side to the base material 12 of the inorganic barrier layer 13 so that an acryloyl group may be exposed by the manufacturing method mentioned above.
  • a (meth) acryloyl group is exposed on the surface (exposed surface) of the inorganic barrier layer 13 opposite to the substrate 12 (FIG. 1).
  • the acryloyl group is exposed).
  • a reactive group that is, alkoxysilyl group
  • a reactive group that is, alkoxysilyl group
  • alkoxysilyl group other than the (meth) acryloyl group of the (meth) acryloyl group-containing silane coupling agent is chemically bonded (covalent bond) to the constituent material of the inorganic barrier layer.
  • (meth) acryloyl groups are exposed on the surface of the inorganic barrier layer.
  • the region where the (meth) acryloyl group above the surface of the inorganic barrier layer 13 in FIG. 1 is present that is, the coating film obtained through the drying step; the region 14 shown in FIG. Also referred to as “adhesive layer”.
  • an “adhesion layer” can be used even with an observation means such as a transmission electron microscope (TEM). It should be noted that it may not be observed as a layer having a certain thickness independent of the inorganic barrier layer 13.
  • the adhesive layer is as thin as possible, and it is preferable that the film thickness be such that the presence of the adhesive layer cannot be confirmed even by observation means such as TEM (for example, 20 nm or less).
  • observation means such as TEM (for example, 20 nm or less).
  • the (meth) acryloyl group contained in the silane coupling agent can be sufficiently oriented on the surface of the adhesive layer, and the risk of the adhesive layer peeling off due to cohesive failure is also reduced.
  • the ultraviolet curable resin layer disposed particularly adjacent thereto is a quantum dot layer (light emitting layer).
  • the deterioration of the layer can be sufficiently prevented, which is preferable.
  • the (meth) acryloyl group is exposed on the surface of the inorganic barrier layer 13 means that the surface layer is scraped off and measured by pyrolysis gas chromatography, as described in the Examples section below. It is possible to confirm by performing and comparing with the standard.
  • the gas barrier film of the present invention can be used for various applications, but for applications where an ultraviolet curable resin layer is provided so as to be adjacent to the exposed surface of the inorganic barrier layer (the (meth) acryloyl group is exposed).
  • an ultraviolet curable resin layer is not particularly limited as long as it is a layer made of a cured product of an ultraviolet curable resin, but as a function thereof, in addition to a protective layer for protecting the inorganic barrier layer, a quantum dot (semiconductor nanoparticle) is used.
  • grains is mentioned.
  • quantum dots semiconductor nanoparticles
  • the UV curable resin layer is a quantum dot layer (light emitting layer)
  • two gas barrier films are used to form an inorganic barrier.
  • a laminated body (light emitting body) formed by sandwiching the quantum dot layer (light emitting layer) so that the layer is disposed on the quantum dot layer (light emitting layer) side is preferable.
  • the gas barrier film according to the present invention a configuration in which the above-described quantum dot layer (light emitting layer) is disposed adjacent to the inorganic barrier property will be described in detail.
  • the quantum dot layer (light emitting layer) usually contains 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 quantum dot layer (light emitting layer) is preferably 0.01 to 50% by mass with respect to the total mass of the quantum dot layer (light emitting layer), 0.5 to 30% by mass is more preferable, and 2.0 to 25% by mass is even more preferable. 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, CdS is 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 dispersibility of the semiconductor nanoparticles in the coating liquid for forming the quantum dot layer (light emitting layer) can be made particularly excellent.
  • the shape can be made higher in sphericity, the particle size distribution can be made sharper, and the light emission characteristics of the semiconductor nanoparticles can be made particularly excellent.
  • 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.
  • the ultraviolet curable resin for example, urethane (meth) acrylate resin, polyester (meth) acrylate resin, epoxy (meth) acrylate resin, polyol (meth) acrylate resin, or epoxy resin is preferably used.
  • urethane (meth) acrylate resin polyester (meth) acrylate resin, epoxy (meth) acrylate resin, polyol (meth) acrylate resin, or epoxy resin is preferably used.
  • Specific examples of these include “(meth) acryloyl group-containing compounds other than the (meth) acryloyl group-containing silane coupling agent” described above as the constituent material of the adhesive layer (that is, polyol poly (meth) acrylate, epoxy (meth) Acrylate, urethane (meth) acrylate, (meth) acrylic monomer) and the like.
  • an epoxy (meth) acrylate resin for example, Unidic (registered trademark) V-5500 ( DIC Corporation)
  • urethane (meth) acrylate resins are preferably used.
  • 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.
  • a method for forming a quantum dot layer (light emitting layer) will be described by taking a laminated body (light emitting body) in which a quantum dot layer (light emitting layer) is sandwiched between two gas barrier films according to the present invention as an example.
  • Emissive layer After applying the coating solution for formation, it is dried, and another gas barrier film according to the present invention is laminated so that the inorganic barrier layer is adjacent to this coating film.
  • a quantum dot layer (light emitting layer) is formed by performing ultraviolet irradiation treatment, and at the same time, a laminate (light emitting body) in which the quantum dot layer (light emitting layer) is sandwiched between two gas barrier films according to the present invention. It is possible to obtain.
  • the laminated body (light emitting body) including the quantum dot layer (light emitting layer) 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 laminated body (light-emitting body) is provided.
  • the laminated body (light emitting body) according to the present invention can be used as, for example, a high-brightness film disposed between a light source and a polarizing plate in a liquid crystal display (LCD).
  • the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer is a quantum dot layer (light emitting layer) containing semiconductor nanoparticles
  • the use of the gas barrier film according to the present invention has been described.
  • the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer does not contain semiconductor nanoparticles and functions as a simple protective layer for the inorganic barrier layer.
  • an ultraviolet curable resin layer (protective layer) is formed using a coating liquid obtained by removing semiconductor nanoparticles from the components contained in the coating liquid used for forming the quantum dot layer (light emitting layer) described above. can do. In this case, needless to say, it is not necessary to use two gas barrier films.
  • the gas barrier film according to the present invention is used in applications where the ultraviolet curable resin layer and the inorganic barrier layer are adjacent to each other as described above, so that the inorganic barrier layer is adjacent to the inorganic barrier layer when the film is placed under a high temperature and high humidity condition. Decrease in adhesion between the UV curable resin layer is suppressed.
  • the ultraviolet curable resin layer is a quantum dot layer (light-emitting layer) (when the laminate is used as a light-emitting body), it is possible to suppress a decrease in luminance of the light-emitting body. Can be expressed.
  • 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.
  • OPSTAR registered trademark
  • Z7501 diluted with butyl acetate to a solid content concentration of 35%
  • 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.
  • inorganic barrier layer sputtering method (composition SiO x )
  • composition SiO x composition SiO x
  • the laminated film of the base material and the underlayer obtained above was placed in a take-up magnetron sputtering apparatus and evacuated to 3 ⁇ 10 ⁇ 6 Torr. Thereafter, the laminated film was rolled back, sufficiently degassed, and it was confirmed that there was no fluctuation in moisture pressure even when the laminated film was conveyed.
  • a B-doped Si target was used as a sputtering target.
  • Adhesion layer formation acryloyl group-containing silane coupling agent
  • PGME propylene glycol monomethyl ether
  • the film was dried at 65 ° C. for 45 seconds to form an adhesive layer made of an acryloyl group-containing silane coupling agent, and gas barrier film 1 was produced.
  • the dry film thickness of this adhesive layer could not be measured with a transmission electron microscope (TEM) (that is, 20 nm or less).
  • TEM transmission electron microscope
  • 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.
  • a gas barrier film 2 was produced in the same manner as the production of the gas barrier film 1 described above except that the coating film was dried at 80 ° C. for 90 seconds when forming the adhesive layer. In addition, it confirmed that the acryloyl group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 2 similarly to the above.
  • a gas barrier film 3 was produced by the same method as the production of the gas barrier film 1 described above, except that the exposed surface of the inorganic barrier layer was subjected to the following oxygen plasma treatment instead of the corona treatment. .
  • the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 10 °. Further, 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.
  • a gas barrier film 4 was produced in the same manner as the production of the gas barrier film 1 described above except that the following excimer treatment was performed instead of the corona treatment as the hydrophilic treatment of the exposed surface of the inorganic barrier layer.
  • the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 18 °. Further, 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.
  • a gas barrier film 5 was prepared by the same method as the preparation of the gas barrier film 1 described above except that the inorganic barrier layer was formed by the following method.
  • the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 17 °. Further, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 5.
  • inorganic barrier layer vacuum plasma CVD method (composition SiO x C y )
  • 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 SiO x C y ) was formed.
  • a gas barrier film 6 was produced by the same method as the production of the gas barrier film 1 described above except that the inorganic barrier layer was formed by the following method.
  • the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 18 °. Further, 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 6.
  • 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.
  • gas barrier film 7 In forming the adhesive layer, instead of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an acryloyl group-containing silane coupling agent, KBM-503 (3-methacryloxypropyltriethoxysilane, which is a methacryloyl group-containing silane coupling agent, Except for using Shin-Etsu Chemical Co., Ltd.), a gas barrier film 7 was produced in the same manner as the production of the gas barrier film 1 described above. In addition, it confirmed that the methacryloyl group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 7 like the above.
  • KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM-503 3-methacryloxypropyltriethoxysilane, which is a methacryloyl group-containing silane coupling agent
  • gas barrier film 8 The solid composition of the coating solution used in forming the adhesive layer was changed from “KBM-5103 100%” to “KBM-5103 95% and pentaerythritol tetraacrylate (PETA; polyfunctional acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • PETA pentaerythritol tetraacrylate
  • a gas barrier film 8 was produced in the same manner as in the production of the gas barrier film 1 described above except that it was changed to “A-TMMT) 5%”. 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.
  • a gas barrier film 10 was produced in the same manner as the production of the gas barrier film 1 described above except that the corona treatment conditions for hydrophilizing the exposed surface of the inorganic barrier layer were changed as follows. In addition, when the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 22 °. Further, 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 10.
  • a gas barrier film 11 was produced by the same method as the production of the gas barrier film 1 described above, except that the corona treatment conditions for hydrophilizing the exposed surface of the inorganic barrier layer were changed as follows. In addition, when the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 40 °. Further, 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.
  • a gas barrier film 12 was produced in the same manner as the production of the gas barrier film 8 described above, except that the coating film was dried at 60 ° C. for 40 seconds when forming the adhesive 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 12.
  • a gas barrier film 13 was produced in the same manner as the production of the gas barrier film 9 described above except that the coating film for forming the adhesive layer was dried at 60 ° C. for 40 seconds.
  • a gas barrier film 14 was produced in the same manner as in the production of the gas barrier film 1 described above, except that the coating film for forming the adhesive layer was dried at 55 ° C. for 240 seconds. 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 14.
  • gas barrier film 15 Similar to the production of the gas barrier film 8 described above except that when the adhesive layer is formed, the coating amount of the coating liquid is increased so that the dry film thickness (observed by TEM) of the adhesive layer is 30 nm.
  • the gas barrier film 15 was produced by the method described above. In addition, it confirmed that the acryloyl group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 15 like the above.
  • gas barrier film 16 Similar to the production of the gas barrier film 8 described above except that when the adhesive layer is formed, the coating amount of the coating liquid is increased so that the dry film thickness (observed by TEM) of the adhesive layer is 50 nm.
  • the gas barrier film 16 was produced by the method described above. 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.
  • a gas barrier film 17 was prepared by the same method as the preparation of the gas barrier film 1 described above except that the inorganic barrier layer was formed by the following method.
  • the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in the same manner as described above, it was 15 °. Further, 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 17.
  • composition AlO x deposition (composition AlO x)
  • Deposition conditions degree of vacuum in aluminum take-up side chamber: 2.3 ⁇ 10 ⁇ 3 mbar Degree of vacuum in the coating chamber before introducing oxygen: 2.9 ⁇ 10 ⁇ 4 mbar Degree of vacuum in coating chamber after introducing oxygen: 4.3 ⁇ 10 ⁇ 4 mbar Film conveyance speed: 500 m / min.
  • gas barrier film 18 In forming the adhesive layer, instead of KBM-5103 (made by Shin-Etsu Chemical Co., Ltd.), which is an acryloyl group-containing silane coupling agent, KBM-903 (3-aminopropyltrimethoxysilane, Shin-Etsu), which is an amino group-containing silane coupling agent, is used.
  • KBM-5103 made by Shin-Etsu Chemical Co., Ltd.
  • KBM-903 3-aminopropyltrimethoxysilane, Shin-Etsu
  • a gas barrier film 18 was produced by the same method as the production of the gas barrier film 1 described above except that Chemical Industries, Ltd. was used.
  • KBM-403 (3-glycidoxypropyltrimethoxysilane) which is an epoxy group-containing silane coupling agent is used instead of KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) which is an acryloyl group-containing silane coupling agent. Except for using Shin-Etsu Chemical Co., Ltd.), a gas barrier film 19 was produced in the same manner as the production of the gas barrier film 1 described above.
  • 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.
  • resin A prepared above was added to prepare a coating solution for forming a quantum dot layer in which the content of semiconductor nanoparticles was 1% (vs. solid content).
  • the quantum dot layer-forming coating solution prepared above was applied on the adhesive layer of the gas barrier film to form a quantum dot-containing coating film.
  • the same gas barrier film is placed so that the adhesive layer side 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 quantum dot-containing coating film was cured by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp to prepare an evaluation sample.
  • the film thickness of the cured layer of the quantum dot-containing coating film was 100 ⁇ m.
  • the gas barrier films of the examples manufactured by the manufacturing method according to the present invention are arranged so that the inorganic barrier layer is adjacent to the ultraviolet curable resin layer as compared with the gas barrier films of the comparative examples.
  • the inorganic barrier layer is adjacent to the ultraviolet curable resin layer as compared with the gas barrier films of the comparative examples.
  • a decrease in adhesion between the inorganic barrier layer and the ultraviolet curable resin layer can be suppressed.
  • the light emission characteristics of the quantum dot layer are deteriorated (particularly under high temperature and high humidity conditions). It can also be seen that it can be suppressed.
  • the solid content contained in the coating liquid for forming the adhesive layer is composed only of the acryloyl group-containing silane coupling agent, which prevents deterioration in adhesion and gas barrier properties (light emission characteristics) under high temperature and high humidity conditions. It can also be seen that it is particularly preferable from the viewpoint.

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Abstract

La présente invention se rapporte à un moyen qui permet de réduire la détérioration au fil du temps des propriétés de barrière contre les gaz et de l'adhérence entre une couche barrière inorganique et une couche de résine polymérisable aux UV (en particulier dans des conditions de température et d'humidité élevées), lorsque la couche barrière inorganique est utilisée à un emplacement adjacent à la couche de résine polymérisable aux UV. La fabrication d'un film barrière contre les gaz (11) est réalisée au moyen d'un procédé de fabrication qui inclut : une étape de formation de film de revêtement au cours de laquelle un corps laminaire, qui comprend un substrat (12) ainsi qu'une couche barrière inorganique (13) constituée d'un oxyde inorganique et située sur au moins un côté du substrat, a, sur la surface apparente de la couche barrière organique, un film de revêtement formé par dépôt d'une solution de revêtement contenant un solvant et un groupe (méth)acryloyle ; et une étape de séchage au cours de laquelle le film de revêtement est séché. La solution de revêtement utilisée contient au moins 95 % en masse d'agent adhésif au silane par rapport à 100 % en masse représentant la quantité totale de solides dans la solution de revêtement.
PCT/JP2016/056736 2015-03-04 2016-03-04 Procédé de fabrication d'un film barrière contre les gaz WO2016140339A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007269957A (ja) * 2006-03-31 2007-10-18 Fujifilm Corp ガスバリア性フィルムとその製造方法、およびそれを用いた画像表示素子
JP2009196318A (ja) * 2008-02-25 2009-09-03 Fujifilm Corp 積層体とバリア性フィルム基板の製造方法、バリア材料、デバイスおよび光学部材
JP2013226773A (ja) * 2012-03-29 2013-11-07 Mitsubishi Plastics Inc ガスバリア性フィルム
JP2016072422A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 波長変換部材の製造方法、波長変換部材、バックライトユニットおよび液晶表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007269957A (ja) * 2006-03-31 2007-10-18 Fujifilm Corp ガスバリア性フィルムとその製造方法、およびそれを用いた画像表示素子
JP2009196318A (ja) * 2008-02-25 2009-09-03 Fujifilm Corp 積層体とバリア性フィルム基板の製造方法、バリア材料、デバイスおよび光学部材
JP2013226773A (ja) * 2012-03-29 2013-11-07 Mitsubishi Plastics Inc ガスバリア性フィルム
JP2016072422A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 波長変換部材の製造方法、波長変換部材、バックライトユニットおよび液晶表示装置

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