WO2016140338A1 - Gas barrier film - Google Patents

Abstract

Provided is a means of reducing the deterioration over time in gas barrier properties and adhesion between an inorganic barrier layer and a UV-curable resin layer (particularly under high-temperature high-humidity conditions), when the inorganic barrier layer is used in a position adjoining the UV-curable resin layer. This gas barrier film (11) comprises a substrate (12) and an inorganic barrier layer (13) made from an inorganic oxide and positioned on at least one side of the substrate, characterized in that an acryloyl group is exposed on the reverse side of the inorganic barrier layer from the substrate.

Description

Gas barrier film

The present invention relates to 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 an ultraviolet curable resin with ultraviolet rays (UV) may be provided so as to be adjacent to the inorganic barrier layer. An example of such an ultraviolet curable resin layer is a protective layer (hard coat layer) for protecting the surface of the inorganic barrier layer. JP 2013-544018 A discloses a gas barrier film so as to sandwich 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. Is disclosed.

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 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, adhesion between an inorganic oxide thin film (inorganic barrier layer) and a heat-meltable heat-sealable resin is improved. We are trying to improve.

The present inventor has conducted various studies on the performance of the laminate in which the ultraviolet curable resin layer as described above is disposed so as to be adjacent to the inorganic barrier layer made of an inorganic compound disposed on the substrate. 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 present 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 conducted intensive research to solve the above problems. As a result, it has been found that the above problem can be solved by configuring the gas barrier film so that the acryloyl group is exposed on the surface (exposed surface) of the inorganic barrier layer adjacent to the ultraviolet curable resin layer. It came to complete.

That is, according to one aspect of the present invention, there is provided a gas barrier film 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. An acryloyl group is exposed on the surface opposite to the substrate, and a gas barrier film is provided.

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, there is provided a gas barrier film having a base material and an inorganic barrier layer made of an inorganic compound disposed on at least one surface of the base material, wherein the base of the inorganic barrier layer A gas barrier film is provided in which an acryloyl group is exposed on a surface (exposed surface) opposite to a material.

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, the acryloyl group exposed on the exposed surface of the inorganic barrier layer is an ultraviolet curable resin that constitutes the ultraviolet curable resin layer. It is presumed that by forming a chemical bond with the resin, a strong bonding region is formed at the interface, so that the adhesion is improved and the deterioration of the gas barrier property 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.

Hereinafter, embodiments of the present invention will be described. 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”. Further, unless otherwise specified, the measurement of operation and physical properties is performed under the conditions of room temperature (25 ° C.) / Relative humidity 40-50% RH.

<Gas barrier film>
The layer structure of the gas barrier film according to one embodiment of the present invention 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. The inorganic barrier layer 13 is characterized in that the acryloyl group is exposed on the surface (exposed surface) opposite to the substrate 12.

[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 A heat-resistant transparent film (product name: Sila-DEC, manufactured by Chisso Corporation) having a silsesquioxane having a basic skeleton, and a resin film formed by laminating two or more layers of the above resin It can gel.

The thickness of the substrate is not particularly limited, but is preferably 5 to 300 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 used.

The base material according to the present invention is preferably transparent. Since the base material is transparent and the layer formed on the base material is also transparent, it becomes possible to make a transparent gas barrier film, so that it becomes possible to make a transparent substrate such as an organic EL element. It is.

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

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

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

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

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

The inorganic barrier layer obtained by the vacuum plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure, has conditions such as the metal compound (decomposition material), decomposition gas, decomposition temperature, and input power as raw materials. This is preferable because the desired compound can be produced. 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 can 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 having bonds such as Si—N, Si—H, and N—H in their structure, such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y It is. In the present specification, “polysilazane compound” is also abbreviated as “polysilazane”.

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

The polysilazane compound is commercially available in a solution in an organic solvent. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310 manufactured by AZ Electronic Materials Co., Ltd. NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and the like.

Other examples of the polysilazane compound that can be used in the present invention include, but are not limited to, for example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), and a reaction with glycidol. 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 obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), and metal fine particles. Addition of fine metal particles Rishirazan (JP 7-196986), such as, include polysilazane compounds ceramic at low temperatures.

(Silazane compound)
Examples 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 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 may 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) transmittance refers to a process for forming the levels of inorganic thin films can contribute to expressing the ^{1 × 10 -3 g / m 2} · day or less).

The conversion reaction of the silicon compound to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. 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 addition, when a layer is formed 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.

The temperature of the coating film during the heat treatment is preferably adjusted appropriately in the range of 50 to 250 ° C, and more preferably in the range of 50 to 120 ° C.

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

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

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

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

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

In the irradiation of 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.

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

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. .

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used. 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 used and the inorganic barrier layer.

(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 the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. 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 emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm. 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.

Also, 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.

¡Excimer lamps have high light generation efficiency and can be lit 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 perform in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably 10 to 20,000 volume ppm, more preferably 50 to 10,000 volume ppm. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

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

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

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

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.

The inorganic barrier layer preferably contains a nitrogen element or a carbon element from the viewpoints of stress relaxation and absorption of ultraviolet rays used for forming a metal atom-containing layer described later. 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 of the inorganic barrier layer can be controlled by the type and amount of the silicon compound and the like when forming the inorganic barrier layer, and the conditions when modifying the layer containing the silicon compound.

[Adhesive layer]
As shown in FIG. 1, the gas barrier film 11 according to the present invention is characterized in that an acryloyl group is exposed on the surface (exposed surface) opposite to the substrate 12 of the inorganic barrier layer 13. Here, the acryloyl group is an acyl group derived from acrylic acid represented by “CH ₂ ═CH—C (═O) —”.

As shown in FIG. 1, there is no particular limitation on the form in which the acryloyl group is exposed on the exposed surface of the inorganic barrier layer 13. For example, a form in which the acryloyl group is exposed as a result of the acryloyl group-containing compound adhering to the surface of the inorganic barrier layer 13 without a chemical bond is mentioned. Moreover, the reactive group other than the acryloyl group of the acryloyl group-containing compound forms a chemical bond (covalent bond) with the constituent material of the inorganic barrier layer, so that the acryloyl group is exposed. Of these, the latter is preferred. In the following, the region where the acryloyl group above the surface of the inorganic barrier layer 13 in FIG. 1 exists (region 14 shown in FIG. 1) is also referred to as “adhesive layer”. However, in some cases (for example, when an acryloyl group-containing silane coupling agent is used as the acryloyl group-containing compound), even if an observation means such as a transmission electron microscope (TEM) is used, the “adhesion layer” It should be noted that it may not be observed as a layer having a certain thickness independent of the inorganic barrier layer 13. Even in such a case, as long as the acryloyl group is exposed on the surface of the inorganic barrier layer 13, it is included in the technical scope of the present invention. The thinner the adhesive layer is, the better. When the presence of the adhesive layer can be confirmed by an observation means such as TEM, the thickness of the adhesive layer is preferably 50 nm or less, and more preferably 20 nm or less. However, as described above, the thinner the adhesive layer is, the more preferable it is, and it is further preferable that the film thickness be such that the presence of the adhesive layer cannot be confirmed even by observation means such as TEM. In addition, “the 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 checking.

Here, as an example of the acryloyl group-containing compound used for “the form in which the acryloyl group is exposed as a result of the acryloyl group-containing compound adhering to the surface of the inorganic barrier layer 13 without a chemical bond”, acryloyl Among the compounds containing a group, those other than the acryloyl group-containing silane coupling agent described later can be mentioned.

Examples of the acryloyl group-containing compound other than the acryloyl group-containing silane coupling agent include polyol polyacrylate, epoxy acrylate, urethane acrylate, acrylic monomer, and the like.

Polyol polyacrylate is an ester compound of polyol and acrylic acid. The polyol selected here is not particularly limited. For example, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4 -Chain aliphatic polyols such as diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol, hydrogenated polyolefin polyol and the like, and 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 tanol and 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. And polyester polyols such as succinate and polycaprolactone, and α, ω-poly (1,6-hexylene carbonate) diol, α, ω-poly (3-methyl-1,5- Styrene 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 acrylate is a compound obtained by adding 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 acrylate is a compound obtained by reacting polyol, polyisocyanate, and hydroxyl group-containing acrylate, or polyol and isocyanato group-containing acrylate. There are no particular restrictions on the polyol, polyisocyanate, hydroxyl group-containing acrylate, and isocyanato group-containing acrylate selected at this time. The polyol is the same as the polyol used in the polyol polyacrylate. 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 acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2- Hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethylacrylamide and the like can be mentioned. These may be used alone or in combination of two or more. Examples of the isocyanato group-containing acrylate include 2-isocyanatoethyl acrylate. These may be used alone or in combination of two or more.

The acrylic monomer is a compound obtained by removing the polyol polyacrylate, the epoxy acrylate, and the urethane acrylate from the acryloyl group-containing compound.

Examples of acrylic monomers include acryloyl-containing compounds having a cyclic ether group such as glycidyl acrylate and tetrahydrofurfuryl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and dicyclopentanyl acrylate. A monofunctional acryloyl group-containing compound having a cyclic aliphatic group such as dicyclopentanylethyl acrylate, 4-tert-butylcyclohexyl acrylate, lauryl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, Monofunctional acryloyl having a chain aliphatic group such as isooctyl acrylate and isoamyl acrylate Group-containing compounds, monofunctional acryloyl group-containing compounds having aromatic rings such as benzyl acrylate, phenoxyethyl acrylate, polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclodecane dimethanol diacrylate And polyfunctional acryloyl group-containing compounds such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. In the present specification, the monofunctional (polyfunctional) acryloyl group-containing compound is also simply referred to as “monofunctional (polyfunctional) acrylate compound”.

As a method for exposing an acryloyl group to the surface of the inorganic barrier layer 13 by attaching an acryloyl group-containing compound other than the acryloyl group-containing silane coupling agent as described above to the surface of the inorganic barrier layer 13, the acryloyl group-containing compound is used. An example is a method in which a solution in which is dissolved in an appropriate solvent is applied to the surface of the inorganic barrier layer 13 and dried. At this time, a suitable photopolymerization initiator is added to the solution, and the coating solution obtained by applying the solution and drying is subjected to a light irradiation treatment to polymerize a part of the acryloyl group-containing compound. May be. However, if it is completely polymerized, the unreacted acryloyl group contained in the adhesive layer disappears, so the polymerization should not be performed completely.

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

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

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

On the other hand, used for "a form in which acryloyl groups are exposed as a result of chemical groups (covalent bonds) forming with the reactive material other than the acryloyl group of the acryloyl group-containing compound with the constituent material of the inorganic barrier layer" Examples of the acryloyl group-containing compound to be obtained include compounds containing an acryloyl group and an alkoxysilyl group in one molecule. When the inorganic compound constituting the inorganic barrier layer 13 contains a silicon atom (for example, having a composition such as SiO, SiON, or SiOC), a compound containing an acryloyl group and an alkoxysilyl group in one molecule is used as the acryloyl group-containing compound. By using it, the alkoxysilyl site contained in the silane coupling agent can form a siloxane bond with the silicon atom. As a result, the acryloyl group contained in the silane coupling agent forms a chemical bond with the silicon atom contained in the inorganic compound via another atom. By adopting such a configuration, the acryloyl group can be more firmly bonded to the inorganic barrier layer, and as a result, when the ultraviolet curable resin layer is provided adjacent to the inorganic barrier layer, these two layers There is an advantage that the adhesion at the interface can be further improved.

As a compound containing an acryloyl group and an alkoxysilyl group in one molecule, a silane coupling agent containing an acryloyl group (acryloyl group-containing silane coupling agent) is preferably used. Examples of the acryloyl group-containing silane coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. . In addition, as a commercial item of an acryloyl group-containing silane coupling agent, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned. One of these acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination. Examples of the “compound containing an acryloyl group and an alkoxysilyl group in one molecule” other than an acryloyl group-containing silane coupling agent include, for example, polyorganosilsesquioxane having an introduced (meth) acryloyl group, Examples thereof include organic-inorganic hybrid materials such as polysiloxane-modified acrylic resins containing a heavy bond. These materials may be prepared independently with reference to conventionally known knowledge, or commercially available products may be used.

As a method for exposing an acryloyl group on the surface of the inorganic barrier layer 13 using a “compound containing an acryloyl group and an alkoxysilyl group in one molecule” such as an acryloyl group-containing silane coupling agent as described above, the acryloyl group may be exposed. An example is a method in which a solution in which the contained compound is dissolved in a suitable solvent is applied to the surface of the inorganic barrier layer 13 and dried. At this time, examples of the solvent that can be used include the same solvents as described above. When the inorganic compound constituting the inorganic barrier layer 13 contains a silicon atom, an adhesive layer is formed using a “compound containing an acryloyl group and an alkoxysilyl group in one molecule” such as an acryloyl group-containing silane coupling agent. Once formed, the hydrolysis / condensation reaction between the alkoxysilyl group contained in the “compound containing an acryloyl group and an alkoxysilyl group in one molecule” with the silicon atom contained in the inorganic compound as time elapses. Wake up. As a result, the acryloyl group contained in the “compound containing acryloyl group and alkoxysilyl group in one molecule” forms a chemical bond with the silicon atom contained in the inorganic compound via another atom. Become.

Here, when the inorganic compound constituting the inorganic barrier layer 13 contains a silicon atom, the surface of the inorganic barrier layer 13 is increased for the purpose of increasing the reaction points on the inorganic barrier layer 13 side where the hydrolysis / condensation reaction described above occurs. After performing the surface modification treatment, it is preferable to form an adhesive layer using a “compound containing an acryloyl group and an alkoxysilyl group in one molecule”. Here, examples of the surface modification treatment that can be performed to increase the reaction point include oxygen plasma treatment, corona treatment, excimer (vacuum ultraviolet) treatment, and UV ozone treatment. There is no restriction | limiting in particular about the specific method for performing these surface modification processes, A conventionally well-known knowledge can be referred suitably. When such a surface modification treatment is performed, the surface of the inorganic barrier layer is hydrophilized. For example, when the inorganic compound constituting the inorganic barrier layer contains silicon atoms, a large number of silanol groups (—Si—OH groups) are formed. It forms on the surface of the inorganic barrier layer. When the adhesive layer is formed in this state, the silanol group reacts with the alkoxysilyl group contained in the “compound containing acryloyl group and alkoxysilyl group in one molecule” such as an acryloyl group-containing silane coupling agent. It becomes possible to increase the number (density) of acryloyl groups exposed on the surface of the layer. 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.

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

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

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

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

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

As an active energy ray-curable material used for forming the underlayer, specifically, UV curable organic / inorganic hybrid hard coating material manufactured by JSR Corporation OPSTAR (registered trademark) series (polymerizable unsaturated group on silica fine particles) And a compound obtained by bonding an organic compound having a compound (a). 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 resistance 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-epichlorohydride Resins.

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

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

The thickness of the underlayer is not particularly limited, but is preferably in the range of 0.1 to 10 μm.

[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., “X-12-2400” 3% isopropyl alcohol solution) can be used.

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

[Bleed-out prevention layer]
The gas barrier film of the present invention can 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.

[Use of gas barrier film]
Although the gas barrier film of the present invention can be used for various applications, it is preferably used for applications in which an ultraviolet curable resin layer is provided so as to be adjacent to the exposed surface of the inorganic barrier layer (the acryloyl group is exposed). It is done. 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” refers to fine particles having a quantum confinement effect (quantum dot effect) composed of a crystal of a semiconductor material and having a size of several nanometers to several tens of nanometers. The energy level E of such semiconductor nanoparticles is generally expressed by the following formula (1) when the Planck constant is “h”, the effective mass of electrons is “m”, and the radius of the semiconductor nanoparticles is “R”. expressed.

Formula (1) E∝h ² / mR ²
As shown by the 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 the present 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% by mass is more preferable, and 2.0 to 25% by mass is even more preferable. If the content is 0.01% by mass or more, sufficient luminance can be obtained, and if it is 50% by mass or less, an appropriate inter-particle distance of the semiconductor nanoparticles is maintained in the quantum dot layer (light emitting layer). And the quantum size effect can be sufficiently exerted.

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

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

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

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

(1) Constituent material of semiconductor nanoparticles As constituent materials of semiconductor nanoparticles, for example, a simple substance of Group 14 element of periodic table such as carbon, silicon, germanium, tin, etc., Group 15 of periodic table such as phosphorus (black phosphorus), etc. Elemental element simple substance, periodic table group 16 element such as selenium, tellurium, etc., compound consisting of a plurality of periodic table group 14 elements such as silicon carbide (SiC), tin (IV) oxide (SnO ₂ ), tin sulfide ( II, IV) (Sn (II) Sn (IV) S ₃ ), tin sulfide (IV) (SnS ₂ ), tin sulfide (II) (SnS), tin selenide (II) (SnSe), tin telluride ( II) (SnTe), lead sulfide (II) (PbS), lead selenide (II) (PbSe), lead telluride (II) (PbTe) periodic table group 14 elements and periodic table group 16 elements Compounds of boron nitride (BN), lithium Boron nitride (BP), Boron arsenide (BAs), Aluminum nitride (AlN), Aluminum phosphide (AlP), Aluminum arsenide (AlAs), Aluminum antimonide (AlSb), Gallium nitride (GaN), Gallium phosphide Periodic tables of (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), etc. A compound of a group element and a group 15 element of the periodic table (or a group III-V compound semiconductor), aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), gallium selenide _(Ga 2 _Se 3), telluride gallium _(Ga 2 _Te 3), acid Indium _{(In 2 O} 3), indium sulfide _{(In 2 S} 3), indium selenide _(In 2 _Se 3), periodic table Group 13 element and Periodic Table Group 16 such as a telluride, indium _(In 2 Te ₃₎ A compound with an element, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI), etc. Compound, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe), etc. Objects (or II-VI compound semiconductor), arsenic sulfide _{(III) (As 2 S} 3), selenium arsenic _(III) (As 2 _Se 3), tellurium arsenic _(III) (As 2 _Te 3), sulfide antimony _{(III) (Sb 2 S 3} ), selenium antimony _{(III) (Sb 2 Se 3} ), antimony telluride _{(III) (Sb 2 Te 3} ), bismuth sulfide _{(III) (Bi 2 S 3} ), selenium Compounds of periodic table group 15 elements and periodic table group 16 elements such as bismuth (III) iodide (Bi ₂ Se ₃ ) and bismuth telluride (III) (Bi ₂ Te ₃ ), copper oxide (I) (Cu ₂ O), copper (I) selenide (Cu ₂ Se) and other compounds of Group 11 elements and Group 16 elements of the periodic table, copper chloride (I) (CuCl), copper bromide (I) ( CuBr), copper iodide (I (CuI), silver chloride (AgCl), periodic table group 11 elements such as silver bromide (AgBr) and group 17 elements, periodic table group 10 such as nickel oxide (II) (NiO) Compound of element and group 16 element of periodic table, compound of group 9 element of periodic table and group 16 element of periodic table such as cobalt (II) oxide (CoO), cobalt sulfide (II) (CoS), tetraoxide Compounds of Group 8 elements of the periodic table such as triiron (Fe ₃ O ₄ ) and iron sulfide (II) (FeS) and Group 16 elements of the periodic table, Periodic Table 7 of manganese (II) oxide (MnO), etc. Compounds of group elements and group 16 elements of the periodic table, compounds of group 6 elements of the periodic table and group 16 elements of the periodic table such as molybdenum sulfide (IV) (MoS ₂ ), tungsten oxide (IV) (WO ₂ ), etc. , Vanadium oxide (II) (VO), vanadium oxide (IV) _(VO 2), compounds of the periodic table group 5 element and the periodic table group 16 element such as tantalum oxide _{(V) (Ta 2 O 5} ), titanium oxide _{(TiO 2, Ti 2 O 5} , Ti 2 O 3 , Ti ₅ O ₉ etc.) periodic table group 4 element and periodic table group 16 element compound, periodic table group 2 element such as magnesium sulfide (MgS), magnesium selenide (MgSe) and periodic table Compounds with group 16 elements, cadmium (II) chromium (III) (CdCr ₂ O ₄ ), cadmium selenide (II) chromium (III) (CdCr ₂ Se ₄ ), copper (II) chromium (III) sulfide (III) ( CuCr ₂ S _4), chalcogen spinels such as mercury selenide (II) chromium _{(III) (HgCr 2 Se 4} ), although barium titanate (BaTiO ₃₎ can be mentioned, _SnS 2, S Compounds of periodic table group 14 elements such as S, SnSe, SnTe, PbS, PbSe, PbTe, and periodic table group 16 elements, III-V such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, etc. Group 13 semiconductors such as Ga ₂ O ₃ , Ga ₂ S ₃ , Ga ₂ Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ Se ₃ , In ₂ Te ₃ the compounds of the elements and the periodic table group 16 element, ZnO, ZnS, ZnSe, ZnTe , CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, II-VI group compound semiconductor such as _HgTe, as ₂ O _3, as ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te ₃ periodic table group 15 element and periodic table group 16 element compound, MgS, MgSe periodic table group 2 element and periodic table group 16 element Compounds. Among these, Si, Ge, GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO, and CdS are more preferable. Since these substances do not contain highly toxic negative elements, they are excellent in environmental pollution resistance and safety to living organisms, and because a pure spectrum can be stably obtained in the visible light region, optical devices Is advantageous for the formation of In particular, CdSe, ZnSe, and CdS are preferable from the viewpoint of light emission stability, and ZnO and ZnS are preferable from the viewpoint of light emission efficiency, high refractive index, safety, and economy. In addition, these light emitting materials may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The core / shell structure is preferably formed of at least two kinds of compounds, and may form a gradient structure (gradient structure) composed of two or more kinds of compounds. 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. The thickness of the shell region is not particularly limited, but is preferably 0.1 to 10 nm, and more preferably 0.1 to 5 nm.

Generally, 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, trioctylphosphineoxy Organic phosphorus compounds such as tridecylphosphine oxide; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; organic nitrogen compounds such as nitrogen-containing aromatic compounds such as pyridine, lutidine, collidine and quinolines; hexylamine; Aminoalkanes such as octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine; dialkyl sulfides such as dibutyl sulfide; dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide; sulfur-containing aromatics such as thiophene Organic sulfur compounds such as compounds; higher fatty acids such as palmitic acid, stearic acid and oleic acid; alcohols; sorbitan fatty acid esters; fatty acid-modified poly Ester 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 or the like; as a production method in a liquid phase, an aqueous raw material is used, for example, an alkane such as n-heptane, n-octane, isooctane, or benzene. , A reverse micelle method in which crystals are grown in a reverse micelle phase in a non-polar organic solvent such as an aromatic hydrocarbon such as toluene and xylene, and a thermally decomposable raw material as a high-temperature liquid-phase organic medium. Examples thereof include a hot soap method in which crystal growth is performed by injection, and a solution reaction method in which crystal growth is performed at a relatively low temperature using an acid-base reaction as a driving force, as in the hot soap method. Any method can be used from these production methods, and among these, a production method in a liquid phase is preferable. It is possible to exchange with the functional surface modifier described above by an exchange reaction performed in the liquid phase.

(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 “acryloyl group-containing compounds other than acryloyl group-containing silane coupling agents” (that is, polyol polyacrylates, epoxy acrylates, urethane acrylates, acrylic monomers) described above as constituent materials of the adhesive layer, The material which substituted the acryloyl group by the methacryloyl group is mentioned. 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.

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

The thickness of the quantum dot layer (light emitting layer) according to this embodiment is not particularly limited, but is preferably 10 to 500 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, and 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 (light emitting layer) containing semiconductor nanoparticles and ultraviolet curable resin (resin component and photopolymerization initiator) on the surface of the inorganic barrier layer (exposed acryloyl group) of the gas barrier film according to the invention After applying the coating liquid for formation, the film is dried, and another gas barrier film according to the present invention is laminated so that the inorganic barrier layer is adjacent to the coating film. By performing irradiation treatment, a quantum dot layer (light emitting layer) is formed, and at the same time, a laminate (light emitting body) is obtained in which the quantum dot layer (light emitting layer) is sandwiched between two gas barrier films according to the present invention. Door can be.

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).

In the present invention, the case where the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer (the acryloyl group is exposed) is a quantum dot layer (light emitting layer) containing semiconductor nanoparticles is taken as an example. The use of the gas barrier film has been described. On the other hand, when the ultraviolet curable resin layer adjacent to the exposed surface of the inorganic barrier layer (the acryloyl group is exposed) does not contain semiconductor nanoparticles and is a layer that functions as a simple protective layer for the inorganic barrier layer, An ultraviolet curable resin layer (protective layer) can be formed in the same manner as described above 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. it can. In this case, needless to say, it is not necessary to use two gas barrier films.

The gas barrier film according to the present invention is used in applications where the ultraviolet curable resin layer and the inorganic barrier layer are adjacent to each other as described above, so that the inorganic barrier layer is adjacent to the inorganic barrier layer when the film is placed under a high temperature and high humidity condition. Decrease in adhesion between the UV curable resin layer is suppressed. 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)
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, sputtering was performed by setting the temperature of the main roll to room temperature, the input power density to 1 W / cm ² , and the film speed to Vf = 1.0 m / min. An inorganic barrier layer (composition SiO ₂ ) having a thickness of 150 nm was formed.

(Adhesion layer formation: acrylic resin)
In a solution obtained by diluting dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, with butyl acetate to a solid content concentration of 5%, 3% polymerization initiator (BASF Japan, Irgacure (registered) (Trademark) 184) was added to prepare a coating solution for forming an adhesive layer. Next, this adhesive layer forming coating solution was applied to the exposed surface of the inorganic barrier layer with a bar coater so that the dry film thickness was 50 nm, and then dried at 80 ° C. for 1 minute as drying conditions. Next, an ultraviolet irradiation treatment was performed with a high-pressure mercury lamp under conditions of 500 mW / cm ² and 200 mJ / cm ^{2 in} an air atmosphere to form an adhesive layer, and thus a gas barrier film 1 was produced. In addition, the surface layer on the inorganic barrier layer side of the gas barrier film 1 is scraped off, measured by pyrolysis gas chromatography, and checked with the standard, so that the acryloyl group is exposed on the exposed surface of the adhesive layer. It was confirmed.

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

(Formation of adhesive layer: acrylic resin + SiO ₂ particles)
In a solution obtained by diluting dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, with butyl acetate to a solid content concentration of 5%, a polymerization initiator (BASF Japan, Irgacure (registered trademark) 184) is added to the resin solid content of 100%. On the other hand, 3% and ELCOM V-8804 (manufactured by JGC Catalysts & Chemicals Co., Ltd.) as silica (SiO ₂ ) particles were added by 30% with respect to 100% of the resin solid content to prepare a coating solution for forming an adhesive layer. Next, this adhesive layer forming coating solution was applied to the exposed surface of the inorganic barrier layer with a bar coater so that the dry film thickness was 50 nm, and then dried at 80 ° C. for 1 minute as drying conditions. Next, an ultraviolet irradiation treatment was performed with a high-pressure mercury lamp under conditions of 500 mW / cm ² and 200 mJ / cm ^{2 in} an air atmosphere to form an adhesive layer.

[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 adhesive layer was formed by the following method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 3.

(Adhesion layer formation: acryloyl group-containing silane coupling agent / acrylic resin (lamination))
A coating solution obtained by diluting acryloyl group-containing silane coupling agent KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) with propylene glycol monomethyl ether (PGME) to a solid content concentration of 5% was applied with a bar coater, and then at 80 ° C. By drying for 1 minute, an adhesive layer (lower layer) made of an acryloyl group-containing silane coupling agent was formed. In addition, although the film thickness of this contact bonding layer (lower layer) was not able to be measured with the transmission electron microscope (TEM), it is theoretically 20 nm or less.

Next, in a solution obtained by diluting dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, with butyl acetate to a solid content concentration of 5%, a polymerization initiator (BASF Japan, Irgacure 3% with respect to 100% of the resin solid content) (Registered trademark) 184) was added to prepare a coating solution.

Then, after apply | coating this coating liquid to the exposed surface of the said inorganic barrier layer with a bar coater so that a dry film thickness may be set to 50 nm, drying was performed for 1 minute at 80 degreeC as drying conditions. Then, in an air ^atmosphere, and subjected to ultraviolet irradiation treatment with high-pressure mercury lamp under the condition of 500mW / cm 2, 200mJ / cm 2, to form an adhesive layer (upper layer) to prepare a gas barrier film 3. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 3.

[Preparation of gas barrier film 4]
In the formation of the adhesive layer, the gas barrier film 4 was produced by the same method as the production of the gas barrier film 3 described above, except that the adhesive layer (upper layer) was not formed after the adhesive layer (lower layer) was formed. . In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 4.

[Preparation of gas barrier film 5]
Prior to forming the adhesive layer, the exposed surface of the inorganic barrier layer was subjected to the surface modification treatment (oxygen plasma treatment) by the following method, and was the same as the production of the gas barrier film 2 described above. The gas barrier film 5 was produced by the method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 5.

(Surface modification 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, on the exposed surface of the inorganic barrier layer. Surface modification treatment (oxygen plasma treatment) was performed.

[Preparation of gas barrier film 6]
The gas barrier film described above except that the surface modification treatment (oxygen plasma treatment) similar to the production of the gas barrier film 5 was performed on the exposed surface of the inorganic barrier layer before forming the adhesive layer. A gas barrier film 6 was produced by the same method as in the production of 4. 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 6.

[Preparation of gas barrier film 7]
A gas barrier film 7 was produced by the same method as the production of the gas barrier film 6 described above except that the inorganic barrier layer was formed by the following technique. 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 7.

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

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

[Preparation of gas barrier film 8]
A gas barrier film 8 was produced by the same method as the production of the gas barrier film 6 described above except that the inorganic barrier layer was formed by the following method. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 8.

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

[Preparation of gas barrier film 9]
The same method as the production of the gas barrier film 6 described above, except that the exposed surface of the inorganic barrier layer was subjected to a surface modification treatment (corona treatment) by the following method before forming the adhesive layer. Thus, a gas barrier film 9 was produced. In addition, it was confirmed in the same manner as described above that the acryloyl group was exposed on the exposed surface of the adhesive layer of the gas barrier film 9.

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

[Production of Gas Barrier Film 10]
The same method as the production of the gas barrier film 6 described above, except that the exposed surface of the inorganic barrier layer was subjected to a surface modification treatment (excimer treatment) by the following method before forming the adhesive layer. Thus, a gas barrier film 10 was produced. In addition, it confirmed that the acryloyl group was exposed on the exposed surface of the contact bonding layer of the gas barrier film 10 like the above.

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

[Preparation of gas barrier film 11]
In the formation of the adhesive layer, in place of dipentaerythritol hexaacrylate, which is a polyfunctional acrylate compound, trimethylolpropane trimethacrylate (TMPT) (manufactured by Shin-Nakamura Chemical Co., Ltd.), which is a polyfunctional methacrylate compound, was used. A gas barrier film 11 was produced by the same method as the production of the gas barrier film 2 described above.

[Preparation of gas barrier film 12]
As described above, KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a methacryloyl group-containing silane coupling agent, was used instead of KBM-5103, which is an acryloyl group-containing silane coupling agent, in the formation of the adhesive layer. A gas barrier film 12 was produced in the same manner as the production of the gas barrier film 4.
[Preparation of gas barrier film 13]
The adhesive layer was formed as described above, except that KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.), a vinyl group-containing silane coupling agent, was used instead of KBM-5103, which is an acryloyl group-containing silane coupling agent. A gas barrier film 13 was produced in the same manner as the production of the gas barrier film 4.

[Preparation of gas barrier film 14]
In the formation of the adhesive layer, the gas barrier described above was used except that KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an amino group-containing silane coupling agent, was used instead of KBM-5103, which is an acryloyl group-containing silane coupling agent. The gas barrier film 14 was produced by the same method as the production of the conductive film 4.

<< Evaluation of gas barrier film >>
The gas barrier films 1 to 14 produced above were evaluated for adhesion and barrier properties when an ultraviolet curable resin layer was provided adjacent to the adhesive layer according to the following method.

(Preparation of Adhesion Evaluation Sample A: When UV-curable resin layer is a protective layer)
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. This resin A is applied on the adhesive layer of the gas barrier film, and then arranged so that the adhesive layer side of the same gas barrier film is in contact with the layer made of resin A (a layer made of resin A with two gas barrier films) The resin A was cured by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp under the conditions of 800 mW / cm ² and 300 mJ / cm ² to prepare an adhesive evaluation sample A. The film thickness of the ultraviolet curable resin layer made of resin A was 50 μm.

(Preparation of Adhesion Evaluation Sample B: When the UV-curable resin layer is a quantum dot layer)
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, the resin A prepared in the preparation of the adhesion evaluation sample A was added to prepare a coating solution for forming a quantum dot layer in which the content of semiconductor nanoparticles was 1% (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 . Then, the quantum dot-containing coating film was cured by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp to produce an adhesion evaluation sample B. The film thickness of the cured layer of the quantum dot-containing coating film was 100 μm.

(Evaluation of adhesion)
About evaluation sample A and evaluation sample B produced above, after leaving still for 500 hours under high-temperature, high-humidity conditions (60 ° C. and 90% RH), adhesion between the inorganic barrier layer and the ultraviolet curable resin layer in each sample Sex 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:
1: Peel strength is less than 2N;
2: Peel strength is 2N or more and less than 3N;
3: The peel strength is 3N or more and less than 4N;
4: Peel strength is 4N or more and less than 5N;
5: 5 N or more (not measurable: the substrate was destroyed and could not be evaluated).

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

From the results of Table 1 above, the gas barrier films (No. 1 to 10) according to the present invention are films having no such structure (No. 1) because the acryloyl group is exposed on the exposed surface of the inorganic barrier layer. 11-14), a decrease in adhesion between the inorganic barrier layer and the UV curable resin layer adjacent to the film when the film is placed under a high temperature and high humidity condition is suppressed, and UV curing is achieved. It turns out that the fall of the brightness | luminance in case a resin layer is a quantum dot layer can also be suppressed.

This application is based on Japanese Patent Application No. 2015-043013 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)

1. A substrate;
   An inorganic barrier layer made of an inorganic compound, disposed on at least one surface of the substrate;
   A gas barrier film having
   A gas barrier film, wherein an acryloyl group is exposed on a surface of the inorganic barrier layer opposite to the substrate.
2. The gas barrier film according to claim 1, wherein the inorganic compound contains a silicon atom, and the acryloyl group forms a chemical bond with the silicon atom via another atom.
3. The gas barrier film according to claim 1 or 2, wherein the acryloyl group and the silicon atom are derived from a compound containing an acryloyl group and an alkoxysilyl group in one molecule.
4. The gas barrier film according to claim 3, wherein the compound is an acryloyl group-containing silane coupling agent.
5. The gas barrier film according to any one of claims 1 to 4, wherein the inorganic compound is a silicon compound having a composition of SiO, SiON or SiOC.

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