JPWO2016140339A1 - Method for producing gas barrier film - Google Patents

Abstract

When the inorganic barrier layer is used so as to be adjacent to the ultraviolet curable resin layer, the adhesion between the inorganic barrier layer and the ultraviolet curable resin layer (particularly under high temperature and high humidity conditions) and gas barrier properties Provided is a means capable of suppressing a decrease over time. (Meth) on the exposed surface of the inorganic barrier layer of the laminate having a base material (12) and an inorganic barrier layer (13) made of an inorganic oxide disposed on at least one surface of the base material. A gas barrier film (11) produced by a production method comprising a coating film forming step of applying a coating solution containing a silane coupling agent containing an acryloyl group and a solvent to form a coating film, and a drying step of drying the coating film. Is used, the coating solution contains 95% by mass or more of the content of the silane coupling agent with respect to 100% by mass of the total solid content of the coating solution. [Selection] Figure 1

Description

  The present invention relates to a method for producing a gas barrier film.

  In the fields of food, packaging materials, pharmaceuticals, etc., it has been a relatively simple method to transmit water vapor, oxygen, etc. by providing a deposition film made of an inorganic compound such as a metal oxide or a coating film made of a resin on the surface of a resin film. A gas barrier film having a gas barrier layer (inorganic barrier layer) to prevent is known. In recent years, in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), organic electroluminescence (EL), quantum dots (QD), etc., the purpose is to make them light and difficult to break. There is an increasing demand for gas barrier films using a resin base material.

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

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

  This inventor performed various examination about the performance of the laminated body which has arrange | positioned the above-mentioned ultraviolet curable resin layer so that it may adjoin to the inorganic barrier layer which consists of an inorganic compound arrange | positioned on a base material. As a result, when 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 It has been found that 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.

  Therefore, the inventor further sought out means for improving the adhesion between the inorganic barrier layer and the ultraviolet curable resin layer. In that process, 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. Here, when the ultraviolet curable resin layer is a protective layer (hard coat layer), if the adhesiveness is not sufficient, the protective effect by the protective layer may be reduced. In addition, when the ultraviolet curable resin layer is a quantum dot layer, if 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).

  The present inventor has intensively studied to solve the above problems. As a result, 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.

  That is, according to one form of this invention, the manufacturing method of a gas barrier film is provided. The manufacturing method 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). And 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.

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

  According to one aspect of the present invention, 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.

  As described above, according to the gas barrier film of the present invention, 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). Here, although the mechanism by which the above-described effects by the configuration of the present invention are exhibited is not completely clear, in the gas barrier film produced by the production method according to the present invention, 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.

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

<Method for producing gas barrier film>
Hereinafter, a method for producing a gas barrier film according to an embodiment of the present invention will be described in the order of a coating film forming step, an (optional) hydrophilization treatment step, and a drying step.

≪Film formation process≫
In this step, 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. Below, the structure of the "laminated body which has a base material and an inorganic barrier layer" prepared before apply | coating the said coating liquid is demonstrated first.

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

  For example, poly (meth) acrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP ), Polystyrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, and other resin films, organic-inorganic hybrid structures Heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having a basic skeleton as well as a resin film formed by laminating two or more layers of the above resin. Rukoto can.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The substrate is heated by this ultraviolet irradiation, and O contributes to ceramicization (silica conversion). ₂And H₂O, the ultraviolet absorber, and the polysilazane itself are excited and activated, so that the polysilazane is excited to promote the conversion of the polysilazane into a ceramic, and the resulting inorganic barrier layer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

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

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

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

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

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

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

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

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

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

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

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

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

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

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

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

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

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

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

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

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

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

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

[Other parts]
Although 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. For example, between 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.

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

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

[Underlayer (smooth layer, primer layer)]
For example, an underlayer (smooth layer, primer layer) 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.

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

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

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

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

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

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

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

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

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

  In this step (coating film forming step), a coating solution containing a silane coupling agent containing a (meth) acryloyl group and a solvent on the exposed surface of the inorganic barrier layer of the laminate having the substrate and the inorganic barrier layer described above. Is applied to form a coating film. Below, the component of the "coating liquid" used in this process is demonstrated.

(solvent)
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 of the (meth) acryloyl group-containing silane coupling agent 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. In the production method according to the present invention, it is essential that 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%.

  Thus, 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. When 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. When a coating film is formed and dried using a coupling agent, 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. Thereby, 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. By adopting such a configuration, the (meth) acryloyl group can be more firmly connected with the inorganic barrier layer, and as a result, when the ultraviolet curable resin layer is provided adjacent to the inorganic barrier layer, There is an advantage that the adhesion at the interface between these two layers can be further improved.

  The solid content of the coating solution may include components other than the silane coupling agent. Examples of 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, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4 -Chain aliphatic polyols such as diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol, hydrogenated polyolefin polyol, and more, 1,4-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, tricyclo [5.2.1.0 ^{2, 6]} Dekanji Examples include polyols having an alicyclic structure such as butanol, 2-methylcyclohexane-1,1-dimethanol, and further trimer triol, p-xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct And polyols having an aromatic ring such as biphenolethylene oxide adduct, and further polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and further, polyhexamethylene adipate and polyhexamethylene. Examples include polyester polyols such as succinate and polycaprolactone, and α, ω-poly (1,6-hexylene carbonate) diol, α, ω-poly (3-methyl-1,5- Acetylene carbonate) diol, α, ω-poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, α, ω-poly [(1,9-nonylene: 2-methyl-1,8 (Octylene) carbonate] (poly) carbonate diols such as diols. These may be used alone or in combination of two or more.

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

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

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

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

  When a (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent as described above is used in combination with a (meth) acryloyl group-containing silane coupling agent, 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. However, if the polymerization is complete, the unreacted (meth) acryloyl group contained in the adhesive layer disappears, so the polymerization should not be performed completely. A conventionally known polymerization inhibitor may be added for the purpose of preventing unintentional polymerization of the (meth) acryloyl group-containing compound.

  Here, 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 rays, and ultraviolet rays. Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, tri Phenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, -Isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. Moreover, a metallocene compound can also be used as a photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  However, in the present invention, as described above, it is essential that 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. . For this reason, even if a (meth) acryloyl group-containing compound other than the (meth) acryloyl group-containing silane coupling agent is contained, the content is at most 5% by mass or less with respect to 100% by mass of the solid content in the coating solution. When 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.

  There is no restriction | limiting in particular about the method of apply | coating the said coating liquid to the exposed surface of the inorganic barrier layer of the said laminated body, A conventionally well-known coating means can be employ | adopted suitably.

≪Hydrophilic treatment process≫
In the method for producing a gas barrier film according to the present invention, it is preferable to perform a step (hydrophilization treatment step) for hydrophilizing the exposed surface of the inorganic barrier layer before the coating film forming step described above. Here, 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. In addition, although there is no restriction | limiting in particular about the lower limit of the contact angle with respect to water, From a viewpoint of preventing the water immersion to the lower layer of an inorganic barrier layer, in order to improve the adhesiveness of an inorganic barrier layer and an ultraviolet curable resin layer, Preferably it is preferable. It is 2 ° or more.

  Here, specific examples of the hydrophilic treatment include oxygen plasma treatment, corona treatment, excimer (vacuum ultraviolet) treatment, UV ozone treatment, and the like. There is no restriction | limiting in particular about the specific method for performing these processes, A conventionally well-known knowledge can be referred suitably. When such a hydrophilization treatment is performed, the surface of the inorganic barrier layer is hydrophilized. For example, when the inorganic compound constituting the inorganic barrier layer contains a silicon atom, a large number of silanol groups (—Si—OH groups) are inorganic. It forms on the surface of the barrier layer. When the coating film forming step is carried out in this state, 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. As a result, when 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.

≪Drying process≫
In the method for producing a gas barrier film according to the present invention, a step (drying step) of drying the coating film formed in the above-described coating film forming step is performed.

  There is no restriction | limiting in particular about the drying means employ | adopted in a drying process, A conventionally well-known knowledge can be referred suitably. 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 | limiting in particular about the upper limit of drying temperature, It is preferable that it is 300 degrees C or less from a viewpoint of setting it as the temperature below the phase transition temperature of a base material. According to the study by the present inventors, a gas barrier film production method having performance and process suitability similar to that of a drying process at 80 ° C. is provided by setting the drying temperature condition of 60 ° C. or more. It has been found. The drying time is preferably 40 seconds or longer, more preferably 45 seconds or longer. Although there is no restriction | limiting in particular about the upper limit of drying time, From a viewpoint of implement | achieving high productivity, it is preferable that 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. In particular, when using the roll-to-roll method, 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. Specifically, by adopting drying conditions of 60 ° C. or higher and 45 seconds or longer, 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.

<Configuration of gas barrier film>
The layer structure of the gas barrier film according to one embodiment of the present invention manufactured by the manufacturing method described above will be described with reference to FIG.

  In FIG. 1, a gas barrier film 11 according to an embodiment of the present invention 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.

  As shown in FIG. 1, in the gas barrier film 11 according to the present invention, a (meth) acryloyl group is exposed on the surface (exposed surface) of the inorganic barrier layer 13 opposite to the substrate 12 (FIG. 1). In the figure, the acryloyl group is exposed). More specifically, a reactive group (that is, 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. As a result, (meth) acryloyl groups are exposed on the surface of the inorganic barrier layer. In this specification, 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”. However, in some cases, as a result of forming a coating film made of a coating solution containing a (meth) acryloyl group-containing silane coupling agent, 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. In addition, it is preferable that 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). By adopting such a configuration, 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. . In addition, since such a configuration makes it difficult for water vapor and oxygen to enter from the side surface of the adhesive layer, the ultraviolet curable resin layer disposed particularly adjacent thereto is a quantum dot layer (light emitting layer). In such a case, the deterioration of the layer can be sufficiently prevented, which is preferable. Here, “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.

[Use of gas barrier film]
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). Preferably used. The 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. The function as a quantum dot layer (light emitting layer) containing particle | grains is mentioned. Since quantum dots (semiconductor nanoparticles) are easily deteriorated by contact with water vapor or oxygen, when 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. Hereinafter, as a preferred embodiment of 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.

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

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

  In this embodiment, the content of the semiconductor nanoparticles contained in the 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 mass% is more preferable, and 2.0-25 mass% is further 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 an average particle diameter corresponding to the target emission color. For example, when it is desired to obtain red light emission, the average particle diameter of the semiconductor nanoparticles is preferably 3.0 to 20 nm, and when it is desired to obtain green light emission, it is preferably 1.5 to 10 nm. When it is desired to obtain blue light emission, the thickness is preferably 1.0 to 3.0 nm.

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

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

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

  (1) Constituent materials of semiconductor nanoparticles
  As a constituent material of the semiconductor nanoparticles, for example, a simple substance of Group 14 element of the periodic table such as carbon, silicon, germanium, tin, a simple substance of Group 15 element of the periodic table such as phosphorus (black phosphorus), selenium, tellurium, etc. A simple substance of Group 16 element of the periodic table, a compound comprising a plurality of Group 14 elements of the periodic table such as silicon carbide (SiC), tin (IV) oxide (SnO₂), Tin sulfide (II, IV) (Sn (II) Sn (IV) S)₃), Tin sulfide (IV) (SnS)₂), Tin (II) sulfide (SnS), tin (II) selenide (SnSe), tin (II) telluride (SnTe), lead (II) sulfide (PbS), lead (II) selenide (PbSe), Compound of periodic table group 14 element and periodic table group 16 element such as lead telluride (II) (PbTe), boron nitride (BN), boron phosphide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb) ), Indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), etc. Group 13 elements and compounds of the periodic table Group 15 element (or group III-V compound semiconductor), aluminum sulfide (Al₂S₃), Aluminum selenide (Al₂Se₃), Gallium sulfide (Ga)₂S₃), Gallium selenide (Ga₂Se₃), Gallium telluride (Ga)₂Te₃), Indium oxide (In₂O₃), Indium sulfide (In₂S₃), Indium selenide (In₂Se₃), Indium telluride (In₂Te₃) And the like, a compound of a periodic table group 13 element and a periodic table group 16 element, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI), etc. Compounds of Group 13 elements and Group 17 elements of the periodic table, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO), sulfide Periodic Table Group 12 elements such as cadmium (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe) and the like. Compounds with group 16 elements (or II-VI group compound semiconductors), arsenic (III) sulfide (As₂S₃), Arsenic selenide (III) (As₂Se₃), Arsenic telluride (III) (As₂Te₃), Antimony (III) sulfide (Sb)₂S₃), Antimony selenide (III) (Sb)₂Se₃), Antimony telluride (III) (Sb)₂Te₃), Bismuth (III) sulfide (Bi)₂S₃), Bismuth selenide (III) (Bi)₂Se₃), Bismuth telluride (III) (Bi)₂Te₃) And the like, a compound of a periodic table group 15 element and a periodic table group 16 element, copper oxide (I) (Cu₂O), copper selenide (I) (Cu₂Compounds of periodic table group 11 elements and periodic table group 16 elements such as Se), copper chloride (I) (CuCl), copper bromide (I) (CuBr), copper iodide (I) (CuI), Compounds of Group 11 elements of the periodic table and elements of Group 17 of the periodic table such as silver chloride (AgCl) and silver bromide (AgBr), Group 10 elements of the periodic table such as nickel (II) (NiO) and the periodic table Compounds of Group 16 elements, compounds of Group 9 elements of the periodic table such as cobalt (II) oxide (CoO), cobalt sulfide (II) (CoS), and Group 16 elements of the periodic table, triiron tetroxide (Fe₃O₄), Compounds of Group 8 elements of the periodic table such as iron (II) sulfide (FeS), and Group 16 elements of the periodic table, Group 7 elements of the periodic table such as manganese (II) (MnO), and Periodic Table 16 Compounds with group elements, molybdenum (IV) sulfide (MoS₂), Tungsten oxide (IV) (WO₂) And the like, a compound of a periodic table group 6 element and a periodic table group 16 element, vanadium oxide (II) (VO), vanadium oxide (IV) (VO)₂), Tantalum oxide (V) (Ta₂O₅) And the like, a compound of a periodic table group 5 element and a periodic table group 16 element, titanium oxide (TiO 2) ₂, Ti₂O₅, Ti₂O₃, Ti₅O₉Etc.) of a periodic table group 4 element and a periodic table group 16 element, magnesium sulfide (MgS), magnesium selenide (MgSe), etc. Compound, cadmium oxide (II) chromium (III) (CdCr₂O₄), Cadmium selenide (II) chromium (III) (CdCr₂Se₄), Copper (II) sulfide, chromium (III) (CuCr₂S₄), Mercury (II) selenide, chromium (III) (HgCr₂Se₄) And other chalcogen spinels, barium titanate (BaTiO)₃) And the like, but SnS₂, SnS, SnSe, SnTe, PbS, PbSe, PbTe, etc., compounds of group 14 elements of the periodic table and group 16 elements of the periodic table, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc. Group V compound semiconductor, Ga₂O₃, Ga₂S₃, Ga₂Se₃, Ga₂Te₃, In₂O₃, In₂S₃, In₂Se₃, In₂Te₃II-VI group compound semiconductors such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, etc. , As₂O₃, As₂S₃, As₂Se₃, As₂Te₃, Sb₂O₃, Sb₂S₃, Sb₂Se₃, Sb₂Te₃, Bi₂O₃, Bi₂S₃, Bi₂Se₃, Bi₂Te₃Examples include compounds of Group 15 elements of the periodic table and Group 16 elements of the periodic table, and compounds of Group 2 elements of the periodic table such as MgS and MgSe and Group 16 elements of the periodic table. Among them, Si, Ge, GaN, GaP, InN, InP, Ga₂O₃, Ga₂S₃, In₂O₃, In₂S₃ZnO, ZnS, CdO, and CdS are more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and because a pure spectrum can be stably obtained in the visible light region, optical devices Is advantageous for the formation of In particular, CdSe, ZnSe, and CdS are preferable from the viewpoint of light emission stability, and ZnO and ZnS are preferable from the viewpoint of light emission efficiency, high refractive index, safety, and economy. In addition, these light emitting materials may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As 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. 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. Among these, from the viewpoint of gas permeation suppression (gas permeation from the sheet end face) and the adhesion between the inorganic barrier layer surface, an epoxy (meth) acrylate resin (for example, Unidic (registered trademark) V-5500 ( DIC Corporation)) and urethane (meth) acrylate resins are preferably used.

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

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

(Method of forming quantum dot layer (light emitting layer))
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. Quantum dot layer containing semiconductor nanoparticles and ultraviolet curable resin (resin component and photopolymerization initiator) on the surface of the inorganic barrier layer (exposed (meth) acryloyl group) of the gas barrier film according to the invention ( 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. Finally, 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).

  As described above, as an example, the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer (the (meth) acryloyl group is exposed) 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. On the other hand, when the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer (the (meth) acryloyl group is exposed) does not contain semiconductor nanoparticles and functions as a simple protective layer for the inorganic barrier layer. In the same manner as above, 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 high temperature and high humidity conditions. Decrease in adhesion between the UV curable resin layer is suppressed. In particular, when 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.

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

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

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

(Formation of inorganic barrier layer: sputtering method (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. Here, a B-doped Si target was used as a sputtering target. Thereafter, an O ₂ / Ar mixed gas (O ₂ / Ar = 30/100 (volume%)) was introduced into the tank at 100 sccm. After maintaining the pressure at 8.0 × 10 ⁻⁴ Torr, the main roll temperature is set to room temperature, the input power density is set to 1 W / cm ² , and the film speed is set to Vf = 1.0 m / min. An inorganic barrier layer (composition SiO _x ) having a thickness of 150 nm was formed.

(Inorganic barrier layer surface hydrophilization treatment (corona treatment))
The exposed surface of the inorganic barrier layer formed above was subjected to surface hydrophilization treatment (corona treatment) by the following method. When the contact angle of the exposed surface of the inorganic barrier layer after the surface hydrophilization treatment was measured in accordance with JIS R3257: 1999, it was 15 °.

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

(Adhesion layer formation: acryloyl group-containing silane coupling agent)
A coating solution prepared by diluting acryloyl group-containing silane coupling agent KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) with propylene glycol monomethyl ether (PGME) to a solid content concentration of 5% After coating with a coater, 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). In addition, the surface layer on the inorganic barrier layer side of the gas barrier film 1 is scraped off, measured by pyrolysis gas chromatography, and checked with the standard, so that the acryloyl group is exposed on the exposed surface of the adhesive layer. It was confirmed.

[Preparation of gas barrier film 2]
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.

[Preparation of gas barrier film 3]
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. . 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 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.

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

[Preparation of gas barrier film 4]
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. 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 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.

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

[Preparation of gas barrier film 5]
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. 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 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.

(Formation of 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.

[Preparation of gas barrier film 6]
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. 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 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.

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

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

[Preparation of gas barrier film 7]
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-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.

[Preparation of gas barrier film 8]
From “KBM-5103 100%” to “KBM-5103 95% and pentaerythritol tetraacrylate (PETA; polyfunctional acrylate compound, manufactured by Shin-Nakamura Chemical Co., Ltd.) 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.

[Preparation of gas barrier film 9]
The solid content composition of the coating solution used in forming the adhesive layer was changed from “KBM-5103 100%” to “KBM-5103 90% and pentaerythritol tetraacrylate (polyfunctional acrylate compound; manufactured by Shin-Nakamura Chemical Co., Ltd., A- A gas barrier film 9 was produced in the same manner as in the production of the gas barrier film 1 described above except that it was changed to “TMMT) 10%”.

[Production of Gas Barrier Film 10]
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.

(Surface hydrophilization treatment: Corona treatment (2))
Using a corona treatment apparatus (manufactured by Kasuga Denki Co., Ltd.), hydrophilization treatment of the exposed surface of the inorganic barrier layer (corona) under the conditions of an output of 300 W, an electrode length of 240 mm, a work electrode distance of 3.0 mm, and a conveying speed of 5.5 m / min. Treatment).

[Preparation of gas barrier film 11]
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.

(Surface hydrophilization treatment: Corona treatment (3))
Using a corona treatment device (manufactured by Kasuga Denki), hydrophilization treatment of the exposed surface of the inorganic barrier layer (corona treatment) under the conditions of an output of 300 W, an electrode length of 240 mm, a work electrode distance of 3.0 mm, and a transfer speed of 7 m / min. Went.

[Preparation of gas barrier film 12]
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.

[Preparation of gas barrier film 13]
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.

[Preparation of gas barrier film 14]
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.

[Preparation of 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.

[Preparation of 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.

[Preparation of gas barrier film 17]
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. 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 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.

(Formation of inorganic barrier layer: evaporation method (composition AlO _x ))
By adjusting the oxygen gas supply amount to the exposed surface of the underlayer of the laminated film of the base material and the underlayer obtained above by the reactive vapor deposition method (conditions are as follows) using an EB type vapor deposition device An inorganic barrier layer (composition AlO _x ) was formed by forming an aluminum oxide vapor-deposited film having a thickness of 500 μm while controlling the ultraviolet transmittance at 366 nm to be 88%.

(Deposition conditions)
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 the coating chamber after introducing oxygen: 4.3 × 10 ⁻⁴ mbar
Film conveyance speed: 500 m / min.

[Preparation of gas barrier film 18]
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-903 (3-aminopropyltrimethoxysilane, Shin-Etsu), which is an amino group-containing silane coupling agent, is used. 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.

[Preparation of gas barrier film 19]
In forming the adhesive layer, KBM-5103 (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.

[Production of Gas Barrier Film 20]
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-803 (3-mercaptopropyltrimethoxysilane, Shin-Etsu) containing a mercapto group-containing silane coupling agent A gas barrier film 20 was produced by the same method as the production of the gas barrier film 1 described above except that Chemical Industries, Ltd. was used.

[Preparation of gas barrier film 21]
The solid content composition of the coating solution used in forming the adhesive layer was changed from “KBM-5103 100%” to “KBM-5103 5%, pentaerythritol tetraacrylate (polyfunctional acrylate compound; Shin-Nakamura Chemical Co., Ltd., A- TMMT) 90% and polymerization initiator (BASF Japan, Irgacure (registered trademark) 184) 5% ", and after the drying step, under high pressure under conditions of 700 mW / cm ² and 500 mJ / cm ² in an air atmosphere A gas barrier film 21 was produced in the same manner as in the production of the gas barrier film 1 described above except that an adhesive layer was formed by performing an ultraviolet irradiation treatment with a mercury lamp. The obtained adhesive layer had a dry film thickness (observed by TEM) of 200 nm.

<< Evaluation of gas barrier film >>
About the gas barrier films 1-21 produced above, according to the following method, adhesion between these layers when an ultraviolet curable resin layer (quantum dot layer (light emitting layer)) is provided so as to be adjacent to the adhesive layer, and The light emission characteristics (luminance) from the quantum dot layer (light emitting layer) were evaluated.

(Preparation of evaluation sample)
Resin A was prepared by adding 3% of a polymerization initiator (BASF Japan, Irgacure (registered trademark) 184) to pentaerythritol diacrylate, which is a polyfunctional acrylate compound, with respect to 100% of the resin amount.

  On the other hand, semiconductor nanoparticles (CdSe / ZnS) emitting red and green light were respectively synthesized according to the method described in JP-T-2013-505347. The semiconductor nanoparticles were dispersed in a toluene solvent so that the red component and the green component were 0.75 mg and 4.12 mg, respectively. To this dispersion, 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. Next, 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 μm.

(Evaluation of adhesion)
For each of the evaluation samples prepared above, the inorganic barrier layer and the ultraviolet curable resin layer in each sample immediately after sample preparation and after standing for 200 hours under high-temperature and high-humidity conditions (60 ° C. and 90% RH) The adhesion between them was evaluated. In addition, the sample was cut into a size of 1 inch in length and 20 cm in width, peel strength was measured in the vertical direction, and five-stage evaluation was performed based on the following criteria. The results are shown in Table 1 below:
X: Peel strength is less than 2N;
Δ: Peel strength of 2N or more and less than 3N;
○: Peel strength is 3N or more and less than 4N;
◯: peel strength of 4N or more and less than 5N;
A: 5 N or more (not measurable: the substrate was destroyed and could not be evaluated).

(Evaluation of luminous characteristics (luminance))
For each of the evaluation samples prepared above, the luminance of each sample was measured immediately after the preparation of the sample and after standing for 200 hours under a high-temperature and high-humidity condition (60 ° C. and 90% RH). And 5-step evaluation was performed based on the following reference | standard. The measurement of the luminance, position the evaluation sample B on a blue LED with an emission wavelength of 450 nm, the brightness with high spectral radiance meter was fixed at 10cm a of CS-2000 (manufactured by Konica Minolta Co., Ltd.) ^{(L *)} This was done by measuring. The results are shown in Table 1 below:
X: The reduction rate of luminance is 30% or more;
(Triangle | delta): The fall rate of a brightness | luminance is 20% or more and less than 30%;
○ △: Decrease rate of luminance is 10% or more and less than 20%;
◯: The luminance decrease rate is 5% or more and less than 10%;
A: The reduction rate of luminance is less than 5%.

  From the results of Table 1 above, 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. When it is used, it can be seen that a decrease in adhesion between the inorganic barrier layer and the ultraviolet curable resin layer (particularly under high temperature and high humidity conditions) can be suppressed. Moreover, as a result of being able to suppress the temporal deterioration of the gas barrier property of the inorganic barrier layer, as shown in Table 1 above, the light emission characteristics of the quantum dot layer (light emitting layer) are deteriorated (particularly under high temperature and high humidity conditions). It can also be seen that it can be suppressed.

  In addition, 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.

  This application is based on Japanese Patent Application No. 2015-043014 filed on March 4, 2015, the disclosure of which is incorporated by reference in its entirety.

11 Gas barrier film,
12 substrate,
13 Inorganic barrier layer,
14 Adhesive layer.

Claims (5)

A silane containing a (meth) acryloyl group on the exposed surface of the inorganic barrier layer of a laminate having a base material and an inorganic barrier layer made of an inorganic oxide disposed on at least one surface of the base material A coating film forming step of forming a coating film by applying a coating liquid containing a coupling agent and a solvent;
A drying step of drying the coating film;
Including
The manufacturing method of the gas barrier film whose content of the said silane coupling agent contained in the said coating liquid is 95 mass% or more with respect to 100 mass% of the total amount of the solid content of the said coating liquid.   The method for producing a gas barrier film according to claim 1, further comprising a hydrophilization treatment step in which a contact angle with respect to water of the exposed surface of the inorganic barrier layer is 20 ° or less before the coating film forming step.   The manufacturing method of the gas barrier film of Claim 1 or 2 whose film thickness of the said coating film after the said drying process is 20 nm or less.   The gas barrier film according to any one of claims 1 to 3, wherein the drying condition in the drying step is 60 ° C or higher and 45 seconds or longer, and further includes a winding step of winding the film after the drying step. Manufacturing method.   The method for producing a gas barrier film according to any one of claims 1 to 4, wherein the inorganic oxide is a silicon compound having a composition of SiO, SiON, or SiOC.