JP4437735B2 - Gas barrier film, and display substrate and display using the same - Google Patents

Description

  The present invention relates to a gas barrier film, and more specifically, for example, a gas barrier film suitable for display substrates or display coating applications, resistant to heat during processing and use, and excellent in gas barrier properties, and The present invention relates to a display substrate and a display used.

In the present specification, “ratio”, “part”, “%” and the like indicating the blending are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated.
Also, “barrier” is “barrier”, “EL” is “electroluminescence”, “LCD” is “liquid crystal display”, “panel” is “element”, “PET” is “polyethylene terephthalate”, “PC” Is an abbreviation, functional expression, common name, or industry term for “polycarbonate”.

  (Main application) The main application of the gas barrier film of the present invention is a film substrate for display. In addition to packaging materials for foods and pharmaceuticals, touch panels, film substrates for lighting, film substrates for solar cells, circuits It can be used for a board film substrate, electronic paper, and the like, and is not particularly limited as long as it is an application requiring gas barrier properties.

(Background Art) In recent years, displays of various display systems have been used, and their practical application has been studied. Except for the cathode ray tube type, all of them are aimed at thinning, and moreover, flexible ones have been demanded. Therefore, it has been studied to use a synthetic resin sheet or a synthetic resin film instead of a glass substrate that has conventionally constituted a display. Alternatively, for the purpose of extending the lifetime of the display, a display substrate using a gas barrier film that blocks oxygen and water vapor from the outside world has been studied.
In addition to mechanical strength, smoothness, gas barrier properties, etc., the synthetic resin film as a display substrate material has a process of laminating various layers for imparting a display function to the synthetic resin film, or a gas barrier layer. Heat resistance or moisture resistance is required in the processing to be applied. However, since general synthetic resin films have much lower heat resistance or moisture resistance than glass substrates, heating in the process of forming a metal thin film by vapor deposition, etc., or a heat curing process after coating with a thermosetting resin paint Deformation due to heating, etc., or deformation caused by moisture absorption due to contact with an aqueous solution in a metal thin film etching process or resist development process is unavoidable, and the flatness of the resulting display or gas barrier film is impaired or laminated This causes troubles such as peeling due to deviation from the metal thin film, or deviation from a preset dimension. Further, in a display such as a liquid crystal display panel or an EL display panel, when a formed element is exposed to water vapor, the performance deteriorates, and troubles such as not emitting light occur.
For this reason, the gas barrier film used for displays and display substrates has a heat resistance of 150 ° C. or higher in order to increase the dimensional stability so that it does not easily stretch or bend due to heat generated during processing or use, or tension during heating. In particular, a display such as a liquid crystal display panel or an EL display panel is required to have an ultra-high gas barrier property so that the formed element does not come into contact with water vapor or oxygen to deteriorate the performance.

(Prior Art) Conventionally, a gas barrier film has a gas barrier film composed of two layers, an inorganic compound vapor deposition layer, and a coating layer of a coating agent mainly composed of a water / alcohol mixed solution on a polymer resin substrate. (See, for example, Patent Document 1).
The gas barrier laminate film comprises an inorganic compound vapor-deposited layer, one or more metal alkoxides or hydrolysates thereof, and an isocyanate compound having at least two isocyanate groups in the molecule, on the polymer resin substrate. It is known that the mixed solution is composed of two layers, preferably a coating layer of a coating agent containing tin chloride, melamine, melamine resin, and formaldehyde (for example, see Patent Document 2).
Furthermore, what forms a gas interruption | blocking layer on a transparent heat resistant base material using a sputtering method is known (for example, refer patent document 3).
However, all of Patent Documents 1 to 3 have water resistance and moisture resistance, have flexibility to withstand a certain degree of deformation, and exhibit gas barrier properties, but are described in the examples. Thus, the oxygen permeability is about 1 cc / m ² · day · atm, the water vapor permeability is about 0.1 g / m ² · day, and the oxygen permeability is about 0.3 cc / m ² · day · atm. There is a drawback that it is insufficient to prevent the deterioration of the light emitting layer of the organic EL device, etc., and further, the heat resistance of 150 ° C. or more, the chemical resistance, and the low linear expansion are described and referred to. Absent.
In Patent Document 4, there is no description or mention about the heat resistance, optical anisotropy, chemical resistance, and gas barrier properties of a coating material necessary as a display substrate.

Japanese Patent Laid-Open No. 7-164591 JP 7-268115 A Japanese Patent Laid-Open No. 11-222508 JP-A-8-54615

  Accordingly, the present invention has been made to solve such problems. Its purpose is to have a heat resistance of 150 ° C or higher, and it is difficult to stretch and bend due to heat during processing and use, so it has high dimensional stability and high chemical resistance, so it can be used during processing and use. It is possible to form a stable gas barrier film that is unlikely to be altered by chemicals, etc., so it has excellent gas barrier properties such as water vapor and oxygen, and prevents deterioration of the gas barrier property due to substrate stress caused by multilayering of the gas barrier layer and smoothing layer The present invention also provides a gas barrier film having almost no optical anisotropy and excellent light transmittance, and a display substrate and a display using the gas barrier film.

To solve the above problem,
The gas barrier film according to the invention of claim 1 is first smoothed to a curable resin layer on both surfaces of a substrate, to the curable resin layer surface on at least one side, and to the first gas barrier layer and the first gas barrier layer surface on at least one side. The base material is a resin with a deflection temperature under load of 150 ° C. or higher, the linear expansion coefficient of the curable resin layer is 100 ppm / K or lower, and the base material and the curable resin are provided. The refractive index difference n is 0.03 ≦ n ≦ 0.18, and the gas barrier layer is selected from the group consisting of inorganic oxides, inorganic oxynitrides, inorganic oxycarbides, and inorganic oxynitride carbides. There, and the layer smoothing layer contains a cardo polymers, organic functional organic functional group and a silane coupling having a hydrolyzable group agent and the silane coupling agent has Coating a is a layer of coating composition composed of a crosslinkable compound at least as a raw material having an organic functional group which reacts with, or layer containing an epoxy backbone polymer, as a, is obtained by.
The gas barrier film according to the invention of claim 2 is such that a second gas barrier layer is provided on at least one side of the first smoothing layer surface.
The gas barrier film according to the invention of claim 3 is such that a second smoothing layer is provided on at least one side of the second gas barrier layer surface.
The gas barrier film according to the invention of claim 4 is such that the substrate is a linear polymer aromatic polycarbonate having a carbonate skeleton having a deflection temperature under load of 160 ° C. or higher.
The gas barrier film according to the invention of claim 5 is such that the curable resin layer is an ionizing radiation curable resin.
The gas barrier film according to the invention of claim 6 is such that the second gas barrier layer is selected from the group consisting of inorganic oxide, inorganic oxynitride, inorganic oxycarbide and inorganic oxynitride carbide. It is.
The gas barrier film according to the invention of claim 7 is characterized in that the second smoothing layer includes a layer containing a cardo polymer, a layer containing an acrylic skeleton polymer, a silane coupling agent having an organic functional group and a hydrolyzing group, and the silane As a layer that is a coating film of a coating composition composed of at least a raw material of a crosslinkable compound having an organic functional group that reacts with an organic functional group that the coupling agent has, or a layer that contains an epoxy skeleton polymer , That is.
A display substrate according to the invention of claim 8 is formed by using the gas barrier film according to any one of claims 1 to 7.
A display substrate according to the invention of claim 9 is such that a transparent conductive film is formed on the gas barrier layer or the smoothing layer surface of the gas barrier film according to any one of claims 1 to 7.
A display according to a tenth aspect of the present invention is such that the display substrate according to any one of the eighth to ninth aspects is used.
A display according to an eleventh aspect of the invention is such that the display substrate according to any one of the eighth to ninth aspects is used.
A display according to a twelfth aspect of the present invention is made by using the display substrate according to any one of the eighth to ninth aspects.

(Points of the Invention) The inventors of the present invention have made extensive studies and basically, both sides of a resin film substrate having a deflection temperature under load of 150 ° C. or more, particularly preferably an aromatic polycarbonate substrate having a deflection temperature under load of 160 ° C. A curable resin layer in which the linear expansion coefficient of the curable resin layer is 100 ppm / K or less and the refractive index difference n with respect to the base material is 0.03 ≦ n ≦ 0.18, and further a gas barrier layer , One or a plurality of smoothing layers or gas barrier layers / smoothing layers as a set.
First, by providing a curable resin layer having a refractive index difference n of 0.03 ≦ n ≦ 0.18 on both surfaces of an aromatic polycarbonate base material having little optical anisotropy and excellent optical properties, The transmittance can be improved by 2-3%.

Furthermore, by providing a curable resin layer having a linear expansion coefficient of 100 ppm / K or less on both surfaces of an aromatic polycarbonate base material having a high deflection temperature, an inorganic layer (functionally a gas barrier layer provided on the curable resin layer surface) ) Is significantly improved, and heat resistance, particularly heat resistance against repeated heat loads of 150 ° C. or more is improved.
Display processing and assembly are repeatedly subjected to heat load, typically heat of 150 ° C or higher, resulting in loss of flatness, peeling due to misalignment with the laminated inorganic layer, or preset dimensions. There are many dangers such as misalignment, but these are resolved. Of course, the curable resin also needs to be able to withstand the repeated application of heat of 150 ° C. or more like the base material, and the deflection temperature under load after coating the curable resin layer on both sides of the base material is high. It is 150 degreeC or more, Preferably it is 160 degreeC or more, More preferably, it is 180 degreeC or more.

Furthermore, by providing a curable resin layer on both sides of the aromatic polycarbonate substrate, it can be stably formed with good adhesion to the inorganic layer (functionally a gas barrier layer) provided on the curable resin layer surface, Ultra-high gas barrier properties can be expressed. Further, providing the smoothing layer / second gas barrier layer on the gas barrier layer surface synergistically improves the gas barrier property.
Thus, according to the present invention, it has been found that even if a synthetic resin film is used as a base material, the light transmittance, heat resistance, and gas barrier properties can be compatible, and the problems can be solved.

According to the present invention of claim 1, even if a plurality of layers such as a gas barrier layer and a smoothing layer are provided to enhance gas barrier properties such as water vapor and oxygen, the adhesion between layers is good and the life is long, and the stress relaxation function is also provided. Therefore, deterioration of the gas barrier property due to the base material stress caused by the layer is prevented, and furthermore, by providing a curable resin layer having a refractive index difference n of 0.03 ≦ n ≦ 0.18, a light transmittance is provided. Is improved, and a gas barrier film having excellent light transmittance is provided. In addition, by smoothing the slight protrusions of the base material with the physical properties, the original function of the gas barrier layer is expressed, and a gas barrier film having an extremely high gas barrier property such as water vapor and oxygen is provided. Moreover, by providing one or more pairs of the smoothing layer and the gas barrier layer, the gas barrier film is provided that further enhances the original function of the gas barrier layer and is excellent in gas barrier properties such as water vapor and oxygen. . Furthermore, since the affinity with the coating layer, wettability, and leveling properties are good, the surface after drying becomes smoother by filling, covering, and closing defects such as holes, recesses, and cracks. A gas barrier film having excellent gas barrier properties and high strength and toughness but not particularly brittle even at low temperatures, high hardness and scratch resistance is provided.
According to the second to third aspects of the present invention, in addition to the effect of the first aspect, by providing one or more pairs of the smoothing layer and the gas barrier layer, the original function of the gas barrier layer is further expressed, Provided is a gas barrier film that is extremely superior in gas barrier properties such as water vapor and oxygen.
According to the fourth aspect of the present invention, in addition to the effects of the first to third aspects, high heat resistance provides excellent dimensional stability during processing and use, and almost no optical anisotropy. A gas barrier film excellent in light transmittance is provided.
According to the fifth aspect of the present invention, in addition to the effects of the first to fourth aspects, an existing facility and a gas barrier film that can be stably produced by a known technique are provided.
According to the sixth aspect of the present invention, in addition to the effects of the first to fifth aspects, a gas barrier film having more stable physical properties and capable of being easily produced is provided.
According to the seventh aspect of the present invention, in addition to the effects of the first to sixth aspects, since the affinity with the coated layer, wettability, and leveling properties are good, defects such as holes, recesses, and cracks The gas barrier film has excellent gas barrier properties, high strength and toughness, but does not become brittle even at low temperatures, and has high hardness and scratch resistance. Provided.
According to the present invention of claims 8 to 9, the gas barrier properties such as water vapor and oxygen are extremely high, the heat resistance during processing and use is excellent due to the high heat resistance, and the optical anisotropy is high. There is provided a display substrate having little lightness and excellent light transmittance.
According to the present invention of claim 10, the heat resistance during processing and use is excellent due to high heat resistance, and the dimensional stability during heating is superb. Various display displays having a long life and almost no light transmittance are provided.
According to the present invention of claim 11, the heat resistance during processing and use is excellent due to high heat resistance, and the dimensional stability during heating is superb. A long-lived liquid crystal display with almost no light transmittance is provided.
According to the twelfth aspect of the present invention, the heat resistance during processing and use is excellent due to high heat resistance, and the dimensional stability during heating is superb. There is provided a long-life organic EL display having almost no light transmittance.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing one embodiment of the gas barrier film of the present invention.
FIG. 2 is a cross-sectional view showing one embodiment of the display substrate of the present invention.

(Invention of Product) As shown in FIG. 1, the gas barrier film 10 of the present invention is a linear polymer aromatic polycarbonate having a carbonate skeleton having a deflection temperature under load of 150 ° C. or higher, preferably 160 ° C. or higher. A curable resin layer in which the linear expansion coefficient of the curable resin layer is 100 ppm / K or less and the refractive index difference n from the substrate is 0.03 ≦ n ≦ 0.18 is provided on both surfaces of the substrate. Furthermore, if necessary, one or a plurality of sets of gas barrier layers, smoothing layers, or gas barrier layers / smoothing layers are provided on the surface of the curable resin layer.
That is, the first smoothing layer 15A / first gas barrier layer 13A / curable resin layer 12A / base material 11 / curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B in FIG. The second gas barrier layer 17A / first smoothing layer 15A / first gas barrier layer 13A / curing resin layer 12A / base material 11 / curing resin layer 12B / first gas barrier layer 13B / first smoothing of FIG. Layer 15B / second gas barrier layer 17B, although not shown, second smoothing layer / second gas barrier layer 17A / first smoothing layer 15A / first gas barrier layer 13A / curable resin layer 12A / substrate 11 / Curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B / second gas barrier layer 17B / second smoothing layer, curable resin layer 12A / base material 11 / curable resin layer 12B / first gas barrier Layer 13B / first smoothing 15B / second gas barrier layer 17B, first gas barrier layer 13A / curable resin layer 12A / base material 11 / curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B / second gas barrier layer 17B, etc. It is a layer structure.

However, although the above-described layer configuration has exemplified a symmetrical configuration that may be warped or deformed, it may be at least on one side and may be asymmetrical. In addition, the gas barrier layer / smoothing layer may be set as one set, and the set may be repeatedly stacked, and the gas barrier property can be remarkably improved. However, the larger the number, the better in terms of gas barrier properties. However, since the productivity and the gas barrier properties commensurate with it cannot be obtained, the preferred layer configuration is the second gas barrier layer 17A / first smoothing layer 15A / first gas barrier. Layer 13A / curable resin layer 12A / base material 11 / curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B / second gas barrier layer 17B.
In view of productivity, curable resin layer 12A / base material 11 / curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B / second gas barrier layer 17B are also preferable. Furthermore, laminating four or more layers on one side of the substrate 11 is not preferable from the viewpoint of productivity due to the occurrence of cracks due to the occurrence of film stress, causing deterioration of gas barrier properties, and increasing the number of processing steps.

Furthermore, you may form a stress relaxation layer in the at least one surface side of a base film so that the stress of a film | membrane may be canceled. It is preferable to make the curable resin layer 12 </ b> A and / or the curable resin layer 12 </ b> B have the function of stress relaxation from the viewpoint of ease of adjustment according to the film stress and productivity.
Furthermore, as shown in FIG. 2, by providing a transparent electrode layer 21, an auxiliary electrode layer 23 and other layers as necessary on the smoothing layer or gas barrier layer surface, a display substrate can be obtained. That is, one set of gas barrier layer / smoothing layer or smoothing layer / gas barrier layer is indispensable via a curable resin layer, and other layers are provided or sandwiched between other layers. May be.
Further, the curable resin layer 12A and the curable resin layer 12B, the first gas barrier layer 13A and the first gas barrier layer 13B, the first smoothing layer 15A and the first smoothing layer 15A, and the second gas barrier layer 17A and the second gas barrier layer 17A. The gas barrier layer 17B may be the same or different.

(Materials) The materials used for the gas barrier film of the present invention and the forming method will be described in detail.
(Base Material) The base material 11 of the present invention is a transparent resin film that is thin, light, hard to break, flexible and thin, instead of the conventional thick, heavy and fragile glass substrate display. In order to obtain heat resistance of 150 ° C. or higher, the deflection temperature under load is 150 ° C. or higher, preferably 160 ° C. or higher, and the linear expansion coefficient is 1 ppm as dimensional stability accuracy. About 100 ppm / K, preferably 1 ppm to 80 ppm / K, more preferably 1 to 50 ppm / K.

Examples of transparent resin films include poly (meth) arylate (PAR), polyimide (PI), polyamideimide (PAI), polyethersulfone (PES), polycarbonate (PC), polyetherketone (PEK), polyetherether Examples thereof include fluorine resins such as ketone (PEEK), polyetherimide (PEI), polysiloxane, and ethylene-tetrafluoroethylene copolymer (ETFE).
Further, the thermal properties of the material of the transparent resin film, in particular, the behavior with respect to external force, polyethylene naphthalate resin (PEN) having a deflection temperature under load specified in JIS K 7191, which is a more practical index, of 150 ° C. or higher; 155 ° C., polycarbonate resin; 160 ° C., polyarylate resin; 175 ° C., polyethersulfone resin; 210 ° C., cycloolefin polymer (trade name: “ZEONOR” manufactured by Nippon Zeon Co., Ltd.); 150 ° C., or norbornene resin (JSR Co., Ltd., trade name: “ARTON”); 155 ° C. can be applied, preferably a polycarbonate resin film with little optical anisotropy and a maximum continuous use temperature of 160 ° C. or more, most preferably carbonate ester It is a linear polymer aromatic polycarbonate with a skeleton.

(Curable resin layer) At least one surface of the base material 11 is provided with a curable type on the surface on which the first gas barrier layer 13A or the second gas barrier layer 13B is formed in order to improve wettability and adhesion with the layer. A resin layer 12A and / or a curable resin layer 12B is provided. The curable resin layer 12A and the curable resin layer 12B (collectively referred to as the curable resin layer 12) are also referred to as an adhesion promoting layer, a primer layer, an undercoat layer, an anchor coat layer, or the like depending on the purpose.
In the curable resin layer 12, the refractive index difference n between the curable resin and the substrate is preferably 0.03 ≦ n ≦ 0.18, more preferably 0.06 ≦ n ≦ 0.15. . When the refractive index difference n is less than 0.03, almost no improvement in light transmittance is observed, and when it exceeds 0.18, coating spots are noticeable and the appearance and display image may be distorted. The curable resin layer 12 is an ionizing radiation curable resin, preferably an ultraviolet curable resin that can be used in existing equipment and can be operated in a stable process.
Further, by providing the curable resin layer 12A and the curable resin layer 12B on both sides, the stress generated when the film is formed on only one side is offset or relaxed, and distortion and warpage in post-processing steps including heating ( Therefore, the right-angle accuracy, the dimensional accuracy, and the dimensional accuracy at the partial location can be improved. Further, for example, the problem of alignment required at the time of patterning is eliminated in a subsequent process such as electrode formation. Furthermore, there is no bias in flexibility and there are no problems in use.

(Ionizing radiation curable resin) As the ionizing radiation curable resin, specifically, those having an acrylate functional group, that is, those having an acrylic skeleton and those having an epoxy skeleton are suitable, and the hardness of the coating film In view of heat resistance, solvent resistance, and scratch resistance, a structure having a high cross-linking density is preferred, and bifunctional or higher acrylate monomers such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di Examples thereof include acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. In the above, acrylate and / or methacrylate are described as (meth) acrylate.
The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when it is cured by irradiating with ultraviolet rays, as a photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl Ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate, etc., and n-butylamine, triethylyl as photosensitizers Luamine, poly-n-butylphosphine and the like can be used alone or as a mixture. The addition amount of the photopolymerization initiator and the photosensitizer is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.

  Fine particles may be added to the (fine particle) curable resin layer 12, and silica fine particles or polymer particles are preferably used. Since the refractive index of the substrate is in the range of 1.45 to 1.65, it can be easily adjusted to a desired refractive index by adding particles having an optimal refractive index. The refractive index of the fine particles is preferably in the range of 1.43 to 1.60, which is about the same as that of the polymer binder (curable resin), because the refractive index of the curable resin layer 12 can be easily adjusted.

(Gas barrier layer) Gas barrier layers 13A and 13B (collectively referred to as gas barrier layer 13) are provided on the surface of the curable resin layer 12. The material of the gas barrier layer 13 is not particularly limited as long as it has gas barrier properties. For example, metals such as aluminum, nickel, chromium, iron, cobalt, zinc, gold, silver, copper; silicon, germanium, carbon Semiconductors such as silicon oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, zinc oxide, cerium oxide, hafnium oxide, barium oxide, etc .; silicon nitride, aluminum nitride Nitrides such as boron nitride and magnesium nitride; carbides such as silicon carbide, sulfides and the like can be applied. Further, an oxynitride, an oxycarbide layer further containing carbon, an inorganic nitride carbide layer, an inorganic oxynitride carbide, or the like, which is a composite of two or more selected from them, can also be applied.
Preferred are inorganic oxides (MO _x ) such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, inorganic nitride (MN _y ), inorganic carbide (MC _z ), inorganic oxide carbide ( MO _x C _z ), inorganic nitride carbide (MN _y C _z ), inorganic oxynitride (MO _x N _y ), inorganic oxynitride carbide (MO _x N _y C _z ), and preferable M is Si, Al, Ti Is a metal element. Moreover, it is the thing which added or substituted the metal, the semiconductor, etc. to them, or those mixtures.

  For the composition of the gas barrier layer 13, for example, a surface analyzer such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like is used. By performing elemental analysis of the silicon oxide film using a method of analyzing by ion etching in the depth direction, the above-described composition ratio and physical properties can be confirmed.

(Inorganic oxide) The inorganic oxide film can be called as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is, for example, SiO _x , AlO _x , MgO MO _x (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as such _x is represented by. Moreover, as a range of said x value, silicon (Si) is 0.1-2, aluminum (Al) is 0.1-1.5, magnesium (Mg) is 0.1-1, Calcium (Ca) is 0.1 to 1, potassium (K) is 0.1 to 0.5, tin (Sn) is 0.1 to 2, and sodium (Na) is 0.1 to 0. 5, Boron (B) is 0.1 to 1, 5, Titanium (Ti) is 0.1 to 2, Lead (Pb) is 0.1 to 1, Zirconium (Zr) is 0.1 to 2 Yttrium (Y) can take a value in the range of 0.1 to 1.5. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of x is a completely oxidized value. Preferred metal oxides of the present invention are silicon (Si), aluminum (Al), and titanium (Ti) oxides. The value of x is, for example, silicon (Si) 1.0-2. If 0 is aluminum (Al), 0.5 to 1.5 can be used, and if titanium (Ti), 1.3 to 2.0 can be used.

(Silicon oxide) In the present invention, an inorganic oxide film of silicon oxide formed by a vacuum film formation method using a vapor deposition monomer gas such as an organic silicon compound is a vapor deposition monomer gas such as an organic silicon compound and an oxygen gas or the like. And the reaction product closely adheres to one surface of the base film to form a dense, flexible thin film, and generally has the general formula SiO _x (where x Is a continuous thin film mainly composed of silicon oxide. The inorganic oxide film of silicon oxide is an inorganic silicon oxide film represented by the general formula SiO _x (where x represents a number of 1.3 to 2) in terms of transparency, flame retardancy, and the like. A thin film mainly composed of an oxide film is preferable. The value of x varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. In general, as the value of x decreases, the film itself becomes dense and the oxygen permeability decreases. It becomes yellowish and its transparency is poor.

In addition, the silicon oxide film is mainly composed of silicon oxide, and further contains at least one compound composed of one or more of carbon, hydrogen, silicon, or oxygen, or two or more of these elements by chemical bonding or the like. May be. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc., the raw material organosilicon compound or a derivative thereof is further added. It may be contained by chemical bonds or the like. Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the inorganic oxide film of silicon oxide can be changed by changing the conditions of the vapor deposition process.

  The content of the above-mentioned compound in the silicon oxide film is about 0.1 to 50%, preferably about 5 to 20%. In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the inorganic oxide film of silicon oxide become insufficient, and scratches, cracks, etc. occur due to bending etc. It is easy and it becomes difficult to stably maintain the flame retardancy, and if it exceeds 50%, the flame retardancy required for use in display applications decreases, which is not preferable. Furthermore, in the present invention, in the silicon oxide film, the content of the above compound is preferably decreased from the surface of the silicon oxide inorganic oxide film in the depth direction. On the surface of the material film, impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the base film, the base film and the silicon oxide film It has the advantage that the tight adhesion of the material becomes strong.

(Inorganic nitride) As the inorganic nitride film, a thin film in which a metal nitride is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium Of metal nitrides such as (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) An inorganic nitride film can be used, and a nitride of a metal such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic nitride film can be referred to as a metal nitride such as silicon nitride, aluminum nitride, titanium nitride, etc., and its notation is, for example, MN _y such as SiN _y , AlN _y , TiN _y, etc. (In the formula, M represents a metal element, and the value of y varies depending on the metal element.) Further, the range of the y value is y = 0.1 to 1.3 for silicon (Si), y = 0.1 to 1.1 for aluminum (Al), and y = 0 for titanium (Ti). 0.1 to 1.3 and tin (Sn) can take values in the range of y = 0.1 to 1.3. In the above formula, when y = 0, it is a complete metal and is not transparent and cannot be used. The upper limit of the range of y = is a completely nitrided value. The preferred metal nitride of the present invention is preferably an oxide of silicon (Si), aluminum (Al), or titanium (Ti). The value of y = is, for example, silicon (Si), y = 0.5. -1.3, if aluminum (Al), y = 0.3-1.0, if titanium (Ti), y = 0.5-1.3, if tin (Sn), y = 0. The thing of the range of 5-1.3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 15 nm.

(Inorganic oxynitride film) As the inorganic oxynitride film, a thin film in which a metal oxynitride is basically deposited can be used. For example, silicon (Si), aluminum (Al), magnesium ( Metals such as Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) An inorganic oxynitride film of oxynitride can be used, and a metal oxynitride such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxynitride film can be referred to as a metal oxynitride such as silicon oxynitride, aluminum oxynitride, titanium oxynitride, and the like, for example, SiO _x N _y , AlO _x N _y , TiO _x N _y, etc., represented by MO _x N _y (wherein M represents a metal element, and the values of X and y are different depending on the metal element). Moreover, as a range of said value of x and y, silicon (Si) x = 1.0-2.0, y = 0.1-1.3, aluminum (Al) x = 0.5- 1.0, y = 0.1-1.0, magnesium (Mg) is x = 0.1-1.0, y = 0.1-0.6, calcium (Ca) is x = 0.1 1.0, y = 0.1-0.5, potassium (K) is x = 0.1-0.5, y = 0.1-0.2, tin (Sn) is x = 0.1 2.0, y = 0.1 to 1.3, sodium (Na) x = 0.1 to 0.5, y = 0.1 to 0.2, boron (B) x = 0.1 1.0, y = 0.1-0.5, titanium (Ti) x = 0.1-2.0, y = 0.1-1.3, lead (Pb) x = 0.1 1.0, y = 0.1 to 0.5, zirconium (Zr) is x = 0.1 to 2.0, y = 0.1 .0, yttrium (Y) may have a value in the range of x = 0.1~1.5, y = 0.1~1.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitrides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) And tin (Sn) oxides are preferred, and the values of x and y are, for example, silicon (Si) x = 1.0 to 2.0, y = 0.1 to 1.3, aluminum ( Al) for x = 0.5 to 1.0, y = 0.1 to 1.0, and titanium (Ti) for x = 1.0 to 2.0, y = 0.1 to 1. Those in the range of 3 can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

(Inorganic oxide carbide film) As the inorganic oxide carbide film, any inorganic oxide carbide film can be used as long as it is basically a thin film in which a metal oxide carbide is deposited. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic oxide carbide film of a metal oxycarbide such as Y) can be used, and a metal oxycarbide such as silicon (Si), aluminum (Al), titanium (Ti), or the like is preferable. The inorganic oxide carbide film can be referred to as a metal oxide carbide such as silicon oxide carbide, aluminum oxide carbide, magnesium oxide carbide, etc., and its notation is, for example, SiO _x C _z , AlO _x C _z , TiO _x C _z. Etc., where MO _x C _z (wherein M represents a metal element, and the values of x and z are different depending on the metal element). Moreover, as a range of said x and z value, silicon (Si) is x = 0.1-1.95, z = 0.1-2.0, aluminum (Al) is x = 0.1-0.1. 1.5, z = 0.1-2.0, magnesium (Mg) x = 0.1-1.0, z = 0.1-1.5, calcium (Ca) x = 0.1 1.0, z = 0.1 to 1.5, potassium (K) x = 0.1 to 0.5, z = 0.1 to 1.0, tin (Sn) x = 0.1 2.0, z = 0.1-2.0, sodium (Na) x = 0.1-0.5, z = 0.1-1.0, boron (B) x = 0.1 1.0, z = 0.1-1.5, titanium (Ti) x = 0.1-2.0, z = 0.1-2.0, lead (Pb) x = 0.1 1.0, z = 0.1 to 2.0, zirconium (Zr) is x = 0.1 to 2.0, z = 0.1 2.0, yttrium (Y) may have a value in the range of x = 0.1~1.5, z = 0.1~2.0. In the above formula, when x = 0 and z = 0, the metal oxide is a complete metal and is not transparent and cannot be used. Preferred metal oxide carbides of the present invention include silicon (Si) and aluminum (Al). Titanium (Ti) oxide carbide is preferable, and the values of x and z are, for example, silicon (Si) x = 1.0 to 1.95, z = 0.1 to 2.0, aluminum (Al ) X = 1.0 to 1.5, z = 0.1 to 2.0, and titanium (Ti) x = 1.0 to 2.0, z = 0.1 to 2.0. The ones in the range can be used.

(General formula SiO _x C _z ) A preferable silicon oxide film containing carbon is mainly composed of silicon oxide and further contains a carbon element. In the general formula SiO _x C _z , when the amount of carbon is small (z value is small), the adhesion to the base film is lacking, and when the amount of carbon is large (z value is large), moisture permeability and oxygen permeability are low. Since it becomes large and flame retardancy decreases, it is preferable that x = 0.1 to 1.95 and z = 0.1 to 2.0 in the general formula SiO _x C _z .

(Inorganic nitride carbide film) As the inorganic nitride carbide film, any inorganic nitride carbide film can be used as long as it is basically a thin film obtained by vapor deposition of metal nitride carbide. For example, silicon (Si), aluminum ( Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium ( An inorganic nitride carbide film of a metal nitride carbide such as Y) can be used, and preferably a metal nitride carbide such as silicon (Si), aluminum (Al), titanium (Ti) or the like. The inorganic nitride carbide film can be referred to as a metal nitride carbide such as silicon nitride carbide, aluminum nitride carbide, titanium nitride carbide, etc., and its notation is, for example, SiN _y C _z , AlN _y C _z , TiN _y C _z. MN _y C _z (wherein, M represents a metal element, and the values of y and z are different depending on the metal element). Moreover, as a range of said y and z value, silicon (Si) is y = 0.1-1.3, z = 0.1-2.0, and aluminum (Al) is y = 0.1-0.1. 1.0, z = 0.1-1.5, magnesium (Mg) is y = 0.1-1.0, z = 0.1-1.5, calcium (Ca) is y = 0.1 1.0, z = 0.1 to 1.5, potassium (K) is y = 0.1 to 0.3, z = 0.1 to 1.0, tin (Sn) is y = 0.1 1.3, z = 0.1-2.0, sodium (Na) is y = 0.1-0.3, z = 0.1-1.5, boron (B) is y = 0.1 1.0, z = 0.1-1.5, titanium (Ti) is y = 0.1-1.3, z = 0.1-2.5, lead (Pb) is y = 0.1 1.0, z = 0.1 to 1.5, zirconium (Zr) is y = 0.1 to 1.3, z = 0.1 .0, yttrium (Y) may have a value in the range of y = 0.1~1.0, z = 0.1~2.0. In the above formula, when x = 0, it is a complete metal and is not transparent and cannot be used. Preferred metal nitride carbides of the present invention include silicon (Si), aluminum (Al), titanium (Ti ) Nitrided carbide is preferred, and the values of y and z are, for example, silicon (Si), y = 1.0 to 1.4, z = 0.1 to 2.0, and aluminum (Al). If y = 0.5 to 1.0, z = 0.1 to 2.0, and titanium (Ti), y = 1.0 to 1.3 and z = 0.1 to 2.0. Things can be used. However, even a colored film may be used because it can maintain transparency if it is 3 to 30 nm.

(Inorganic oxynitride carbide film) A preferred inorganic oxynitride (inorganic oxynitride carbide) containing carbon is mainly composed of silicon oxynitride or titanium oxynitride and further contains a carbon element. In the general formula MO _x N _y C _z, low carbon (z value is smaller) lack in adhesion to the base film in case (larger z value) carbon is large when the moisture permeability and the oxygen permeability The degree increases and flame retardancy decreases. Examples of the M element include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y), and the like can be used, and Si, Al, and Ti are preferable. However, even a colored film may be used because it can maintain transparency if it is 3 to 50 nm.

As a preferable inorganic oxynitride carbide, for example, in the general formula SiO _x N _y C _z , x = 0.1 to 1.95, y = 0.1 to 1.2, z = 0.1 to 2.0 It is preferable to do.

Further, in the general formula AlO _x N _y C _z , by setting the composition in the range of x = 0.1 to 1.4, y = 0.1 to 0.9, z = 0.1 to 2.0, The aluminum oxynitride thin film has a low residual carbon component ratio, can suppress degradation of performance due to oxidation of the titanium oxynitride thin film, has high transparency, and has excellent adhesion to CVD materials (base film) Can be obtained.

Furthermore, in the general formula TiO _x N _y C _z , by setting the composition in the range of x = 1.0 to 1.8, y = 0.5 to 1.0, z = 0.3 to 1.5, The titanium oxynitride thin film has a low residual carbon component ratio, can suppress performance degradation due to oxidation of the titanium oxynitride thin film, is highly transparent, and has excellent adhesion to CVD materials (base film) Can be obtained. As a material constituting the thin film layer, an organic titanium compound such as titanium tetrachloride or tetraisopropoxide is suitable. If the x value is less than this range, the Ti—O bond decreases and the film stress increases, peeling from the base film or chipping occurs in the thin film, and the barrier property decreases. Since it progresses and many functional groups are formed, it becomes a thin film lacking in heat resistance and moisture resistance, and flame retardancy deteriorates.
If the y value is less than this range, the film density is small and a dense film cannot be formed, so that the barrier property is lowered, and if it exceeds this range, the Ti-N bond increases and the thin film becomes hard, so lack of flexibility. The barrier property is likely to be lowered by external force, and the flame retardancy is deteriorated.
If the z value is less than this range, the carbon-containing component at the interface with the base film decreases, and the adhesion with the base film decreases. If the z value exceeds this range, the carbon-containing component increases, resulting in film absorption. Coloring occurs.

  The thickness of the gas barrier layer 13 is not particularly limited as long as it is a thickness useful as a gas leakage preventing property (gas barrier property), but is preferably 30 to 10,000 mm, more preferably 100 to 5000 mm, and further preferably 300 to 2500 mm. is there. The transmitted hue and / or reflected hue is preferably colorless, but the color need not be colorless as long as the total light transmittance is 70% or more. If it is less than 30 mm, the gas barrier property as a display substrate is not sufficient, and if it exceeds 10,000 mm, its own stress increases and flexibility is impaired.

  (Manufacturing method of gas barrier layer) The manufacturing method of the gas barrier layer 13 is not particularly limited, but is preferably a method such as a vacuum deposition method, a sputtering method, an ion plating method, a Cat-CVD method, a plasma CVD method, an atmospheric pressure plasma CVD method. Formed by applying the law. Selection may be made in consideration of the type of film forming material, easiness of film forming, process efficiency, and the like. For example, the vapor deposition method uses resistance heating, high-frequency induction heating, beam heating such as electron beam or ion beam, etc., to heat and evaporate the material in the crucible and attach it to a flexible substrate (plastic film, etc.) This is a method for obtaining a thin film. At this time, the heating temperature and the heating method differ depending on the material, purpose, etc., and a reactive vapor deposition method that causes an oxidation reaction or the like can also be used.

  (Smoothing layer) Smoothing layers 15A and 15B (collectively referred to as the smoothing layer 15) are provided on the surface of the gas barrier layer 13. The smoothing layer 15 may be a sol-gel material, an ionizing radiation curable resin, a thermosetting resin, or a photoresist material as long as it is applied for the purpose of flattening the surface, but preferably has a gas barrier function. Or excellent coating performance. In order to improve the coating performance, an ionizing radiation curable resin is preferable, and a resin that undergoes a crosslinking polymerization reaction and changes to a three-dimensional polymer structure when irradiated with ultraviolet rays (UV) or electron beams (EB). That is, an ionizing radiation curable resin obtained by appropriately mixing a reactive prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule, or coating suitability. In consideration of the above, etc. using a liquid composition obtained by mixing a thermoplastic resin such as urethane, polyester, acrylic, butyral, vinyl or the like with the ionizing radiation curable resin as necessary. It can be formed by applying, drying, and curing by a known coating method such as a roll coating method, a Miya bar coating method, or a gravure coating method.

(Ionizing radiation curable resin) As the ionizing radiation curable resin, specifically, those having an acrylate functional group, that is, those having an acrylic skeleton and those having an epoxy skeleton are suitable, and the hardness of the coating film In view of heat resistance, solvent resistance, and scratch resistance, a structure having a high cross-linking density is preferred, and bifunctional or higher acrylate monomers such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di Examples thereof include acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. In the above, acrylate and / or methacrylate are described as (meth) acrylate.
The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when it is cured by irradiating with ultraviolet rays, as a photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl Ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate, etc., and n-butylamine, triethylyl as photosensitizers Luamine, poly-n-butylphosphine and the like can be used alone or as a mixture. The addition amount of the photopolymerization initiator and the photosensitizer is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin. In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, antifoaming agents, thickeners, etc. are added to the coating composition as necessary. can do.

As a coating amount, about 0.5-15 g / m < ² > is suitable as solid content. In addition, as an ultraviolet ray source used for hardening, the light source of an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp can be used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm can be used, and as an electron beam source, a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, or a straight line Various electron beam accelerators such as a type, a dynamitron type, and a high frequency type can be used.

  (Sol-gel method) As a material for the smoothing layer in the present invention, a sol-gel material using a sol-gel method capable of forming a coating film of the same material system is also suitable in order to obtain adhesion to the barrier layer. The sol-gel method is a coating composition comprising at least a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent. It is a method of coating an object and a coating film. Examples of the silane coupling agent having an organic functional group and a hydrolyzable group (hereinafter sometimes simply referred to as a silane coupling agent) include, for example, the following general formula (a) disclosed in JP-A-2001-207130. It is aminoalkyl dialkoxysilane represented by these, or aminoalkyltrialkoxysilane.

（但し、Ａ1はアルキレン基を表す。Ｒ４は水素原子、低級アルキル基、または、下記一般式（ｂ）で表される。）

(However, A1 represents an alkylene group. R4 is represented by a hydrogen atom, a lower alkyl group, or the following general formula (b).)

（ただし、Ａ２は直接結合またはアルキレン基を表し、Ｒ８、Ｒ９は水素原子または低級アルキル基を表す）で表される基を表す。Ｒ５は水素原子または低級アルキル基を表す。Ｒ６は炭素数１〜４のアルキル基、アリール基または不飽和脂肪族残基を表す。分子中にＲ６が複数存在する場合、それらは互いに同一であっても異なっていてもよい。Ｒ７は水素原子、炭素数１〜４のアルキル基またはアシル基を表し、水素原子、炭素数１〜３のアルキル基またはアシル基であることが好ましい。分子中にＲ７が複数存在する場合、それらは互いに同一であっても異なっていてもよい。ただし、Ｒ４、Ｒ５、Ｒ８、Ｒ９のうちの少なくとも一つが水素原子である。ｗは０、１、２のいずれかであり、ｚは１〜３の整数であり、かつｗ＋ｚ＝３である。）

Wherein A2 represents a direct bond or an alkylene group, and R8 and R9 represent a hydrogen atom or a lower alkyl group. R5 represents a hydrogen atom or a lower alkyl group. R6 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or an unsaturated aliphatic residue. When two or more R6 exists in a molecule | numerator, they may mutually be same or different. R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group, and is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group. When two or more R7 exists in a molecule | numerator, they may mutually be same or different. However, at least one of R4, R5, R8, and R9 is a hydrogen atom. w is 0, 1, or 2, z is an integer of 1 to 3, and w + z = 3. )

  Specific examples of the aminoalkyl dialkoxysilane or aminoalkyltrialkoxysilane represented by the above formula (a) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl). ) Γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyl Dibutoxysilane, N-β (aminoethyl) γ-aminopropylethyldimethyl Xisilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylethyldibutoxysilane Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane , Γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ Aminopropyl ethyl dibutoxy silane, .gamma.-aminopropyl triacetoxysilane, and the like, may be used alone or two or more thereof.

  The crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent (sometimes simply referred to as a crosslinkable compound) is a glycidyl group that is a functional group capable of reacting with an amino group. , Carboxyl group, isocyanate group, or oxazoline group, and specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and nonaethylene glycol diester. Glycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neope Diglycidyl ethers such as til glycol diglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl ether; glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) ) Triglycidyl ethers such as isocyanurate and trimethylolpropane triglycidyl ether; tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether; other polyglycidyl ethers or polymers having a glycidyl group as a functional group; tartaric acid and adipic acid Dicarboxylic acids such as; carboxyl-containing polymers such as polyacrylic acid; hexamethylene diisocyanate, xylylene diisocyanate Isocyanates such as: oxazoline-containing polymers; alicyclic epoxy compounds, etc., and one or more of these can be used, but in terms of reactivity, they have two or more glycidyl groups. Are preferably used.

  The amount of the crosslinkable compound used is preferably 0.1 to 300% (mass basis, the same applies hereinafter) with respect to the silane coupling agent, and more preferably 1 to 200%. When the crosslinkable compound is less than 0.1%, the flexibility of the coating film becomes insufficient, and when it exceeds 300%, the gas barrier property may be lowered. The silane coupling agent and the crosslinkable compound are stirred while heating as necessary to obtain a coating composition. By coating and drying the coating composition using the silane coupling agent and the crosslinkable compound as raw materials on the thin film layer 4, hydrolysis and condensation of the silane coupling agent and crosslinking with the crosslinkable compound proceed. Thus, a polysiloxane coating film having a crosslinked structure is obtained.

  The above composition may further contain a silane compound having a hydrolyzable group and not having an organic functional group such as an amino group. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxy Silane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, γ-glycidpropyltrimethoxysilane, γ-glycidpropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. 1 type, or 2 or more types of these can be used.

  When containing a silane compound having the above-mentioned hydrolyzable group and not having an organic functional group such as an amino group, co-hydrolysis of an organic functional group such as an amino group and a silane coupling agent having a hydrolyzable group Condensation and crosslinking with a crosslinkable compound proceed to obtain a polysiloxane coating film having a crosslinked structure.

  The coating composition further comprises a (co) hydrolysis of a silane coupling agent having an organic functional group such as an amino group and a hydrolyzing group and / or a hydrolyzing group and not having an organic functional group such as an amino group. A decomposition condensate may be contained. In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, antifoaming agents, thickeners, etc. are added to the coating composition as necessary. can do.

(Cardopolymer) As a material for the smoothing layer, a cardo polymer is preferably contained. The cardo polymer is a polymer having the following cardo structure, which is synthesized from a monomer having a cardo structure and another polymerizable monomer, and can be applied to a cardo polyester polymer, a cardo acrylic polymer, a cardo epoxy polymer, etc. Is a cardo epoxy polymer. The smoothing layer should just contain the cardo polymer as a main component.
In addition, for the smoothing layer, additives such as plasticizers, fillers, antistatic agents, lubricants, antiblocking agents, antioxidants, UV absorbers, light stabilizers, and the like are modified as necessary. Resin for use may be added.

The cardo polymer has a unique structure called a cardo structure in the main chain skeleton of the polymer, and the cardo structure has a large number of aromatic rings. Due to its steric hindrance, the fluorene skeleton part and the main chain The direction is twisted, so the central carbon atom part can change the bond angle relatively freely, so it is strong and strong, but it is not brittle even at low temperatures, and it has high hardness and scratch resistance. It is estimated that
Moreover, since the layer containing a cardo polymer has a good leveling property, it fills and covers a defect, and the surface after drying becomes smoother. Moreover, since it has good affinity and wettability with the inorganic compound (gas barrier layer 13A of the present invention), it fills, covers, and closes defects such as holes, recesses, and cracks. A super-smoothing function is exhibited by a synergistic effect of leveling properties, and smoothing, that is, Ra and Rmax on the surface can be significantly reduced.
In this way, by increasing the surface smoothness, the gas permeation proceeds to adsorb gas to the surface of the material, dissolve in the material, diffuse in the material, and dissipate to the opposite surface. By reducing the adsorption site (surface area), the adsorption on the surface of the first stage can be greatly reduced, so that the gas barrier property can be remarkably improved.

  (Layer structure of the assembly structure) As described above, the layer structure includes the second gas barrier layer 17A / first smoothing layer 15A / first gas barrier layer 13A / curable resin layer 12A / substrate of FIG. In the case where a plurality of gas barrier layers 17 and / or smoothing layers 15 are formed, such as 11 / curable resin layer 12B / first gas barrier layer 13B / first smoothing layer 15B / second gas barrier layer 17B. The same formation method may be repeated a plurality of times using the same material as the gas barrier layer 17 and / or the smoothing layer 15.

  (Display Substrate) Furthermore, as shown in FIG. 2, the transparent electrode layer 21, the auxiliary electrode layer 23 as required, and the auxiliary electrode layer 23 as necessary, are provided on the surface of the curable resin layer 12, the gas barrier layer 13 or the smoothing layer 15. By providing other layers, the display substrate 20 can be obtained.

  (Solar cell) It is also suitable for application to a solar cell that requires moisture resistance, such as an organic solar cell or a dye-sensitized solar cell, or whose contents need to be protected.

(Display) When the gas barrier film 10 of the present invention is used as the substrate 20 of the display, a layer necessary for each display method can be laminated on either the front or back of the gas barrier film 10, depending on circumstances. Since these layers may be laminated between the base film and the gas barrier layer, the gas barrier film 10 of the present invention has a display function between the base film and the thin film layer. Including a layer for interposing.
The display may be any display using the above-described display substrate. Depth of a plasma display panel (PDP), liquid crystal display (LCD), organic or inorganic electroluminescence display (ELD), field emission display (FED), etc. Therefore, it can be suitably applied to a thin type with a small amount.

(LCD) In general, a liquid crystal display is one in which a transparent electrode is arranged on the inside of two glass substrates, liquid crystal is sandwiched between alignment layers and the like, and the periphery is sealed. Yes, with color filters for colorization. The gas barrier film 10 of the present invention can be applied to the outside of the glass substrate of such a liquid crystal display, or the gas barrier film 10 of the present invention can be used in place of the glass substrate. In particular, if both of the two glass substrates are replaced with the gas barrier film 10 of the present invention, the entire display can be made flexible.
Some types of liquid crystals have optical anisotropy and some epoxy resins cannot be used, but can be applied without using a polarizing plate or by changing the position of the liquid crystal layer. Or a polymer-dispersed liquid crystal.
Plastic liquid crystal is used for displays used in mobile devices such as personal digital assistants, communication devices (cell phones, etc.), notebook personal computers (PCs), and amusements (handy game machines), and is lightweight (about 1/3 of glass) and thin ( About 1/2) glass, durability (about 10 times that of glass), high display capacity, display without parallax (no double image even in reflection mode), etc. It can cope with low power consumption.
The polymer-dispersed liquid crystal is aligned by applying an electric field to small particles of liquid crystal dispersed in the polymer, and is used as an optical shutter. Unlike TN liquid crystal, since it uses a scattering-non-scattering state, in principle, no polarizing plate is required, the polarizing plate is unnecessary and it is brighter, the image display operation speed is faster, the liquid crystal injection process is unnecessary, and the cell gap control is easy. There is an advantage that rubbing is unnecessary, and it can be applied to a projection type.

  (Organic EL) The organic EL display also has a transparent electrode on the inside of two substrates, and, for example, (a) an injection function, (b) a transport function, and (c) a light emission function. The organic EL element layer which consists of a composite layer etc. which laminated | stacked the layer which has each function of these is pinched | interposed, and the circumference | surroundings are sealed. In the case of constituting an EL display, for example, the thin display substrate of the present invention (including the patterned transparent conductive layer and auxiliary electrode layer) / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode. / The layer structure which consists of a sealing layer can be mentioned. The layer structure is not particularly limited, and specifically, anode / light emitting layer / cathode, anode / hole injection layer / light emitting layer / cathode, anode / light emitting layer / electron injection layer / cathode, anode / Many layer structures such as hole injection layer / light emitting layer / electron injection layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode can be handled. It is not limited to this configuration, and may be accompanied by a color filter for colorization or other means (layers). As in the liquid crystal display, the gas barrier film 10 of the present invention can be applied to the outside of the glass substrate, or the gas barrier film 10 of the present invention can be used instead of the glass substrate. If all the glass substrates are replaced with the gas barrier film 10 of the present invention, the entire display can be made flexible. In particular, organic EL elements are chemically unstable due to the use of fluorescent light emission, and are extremely vulnerable to moisture. Therefore, a high water vapor barrier property after a product is desired. In order to ensure the water vapor barrier property of the laminated structure, the substrate film of the gas barrier film preferably has a deflection temperature under load of 150 ° C or higher, preferably 160 ° C or higher.

EXAMPLES Hereinafter, although an Example, a reference example, and a comparative example demonstrate this invention further in detail, it is not limited to this.
The materials and forming methods of the respective layers used in Examples, Reference Examples and Comparative Examples will be described collectively.

(Substrate) As a substrate of Examples , Reference Examples and Comparative Examples , Panlite film AD-5503 having a thickness of 200 μm and a deflection temperature under load of 160 ° C. (manufactured by Teijin Limited, polycarbonate: film trade name) was used.

(Curable resin layer) As the curable resin layer 12, the following UV curable resin composition was applied to the front and back surfaces of the substrate, dried at 120 ° C for 2 minutes, and then ultraviolet ( UV) was irradiated and UV cured to form a curable resin layer having a thickness of 2 μm.
(For Examples or Reference Examples )
<First UV curable resin composition having a refractive index difference of 0.05>
Paracumylphenoxyethylene glycol acrylate: 50 parts from Shin-Nakamura Chemical Co., Ltd. Photopolymerization initiator (Irgacure 184; Ciba Geigy) 5 parts Solvent (toluene) 50 parts The refractive index of the curable resin layer is 1.55 Thus, the difference in refractive index from the substrate was 0.05.
<Second UV curable resin composition having a refractive index difference of 0.09>
Pentaerythritol triacrylate: 50 parts manufactured by Nippon Kayaku Co., Ltd. Photopolymerization initiator (Irgacure 184; manufactured by Ciba Geigy) 2 parts Solvent (toluene) 50 parts The refractive index of the curable resin layer is 1.51, The refractive index difference from the substrate was 0.09.
<Third UV curable resin composition having a refractive index difference of 0.14>
FA129A (nonanediol diacrylate; manufactured by Hitachi Chemical Co., Ltd.) 50 parts Photopolymerization initiator (Irgacure 184; manufactured by Ciba Geigy Co.) 5 parts Solvent (isopropyl alcohol: methyl ethyl ketone = 1: 1) 80 parts The refractive index of the mold resin layer was 1.46, and the difference in refractive index from the substrate was 0.14.
(For comparative example)
-<Fourth UV curable resin composition having a refractive index difference of 0.02 or less>
HR-041 (Nippon Kayaku) 60 parts Photopolymerization initiator (Irgacure 184; Ciba Geigy) 5 parts Solvent (isopropyl alcohol: methyl ethyl ketone = 1: 1) 100 parts Refractive index of the curable resin layer Was 1.60, and the difference in refractive index from the substrate was 0.00.
<Fifth UV curable resin composition having a refractive index difference of 0.18 or more>
-JSR Co., Ltd., trade name: "TM086" 60 parts-Photopolymerization initiator (Irgacure 184; Ciba Geigy) 5 parts-Solvent (toluene) 50 parts The refractive index of the curable resin layer is 1.41 The difference in refractive index from the substrate was 0.19.

(Gas Barrier Layer) The method of forming the gas barrier layer 13 in the examples , reference examples and comparative examples is as follows.
SiOx is placed in a film forming chamber of a magnetron sputtering apparatus, silicon is used as a target, and a gas barrier is formed so that the film thickness of silicon oxide (SiO x, x = 1.6) is 100 nm under the following film forming conditions. A layer was provided.
<Film formation conditions>
Film forming pressure: 2.7 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Oxygen gas flow rate: 10 sccm
・ Applied power: 2.0kW
SiON is disposed in a film forming chamber of a magnetron sputtering apparatus, silicon nitride is used as a target, and a silicon oxynitride (SiOxNy, x = 1.0, y = 0.4) film is formed under the following film forming conditions. A gas barrier layer was provided so as to have a thickness of 100 nm.
<Film formation conditions>
・ Film formation pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Oxygen gas flow rate: 5 sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.2 kW
SiOC was placed in the film formation chamber of the plasma CVD apparatus, HMDSO was used as the source gas, and a gas barrier layer was provided so that the silicon oxide carbide film thickness was 100 nm under the following film formation conditions.
<Film formation conditions>
・ Film pressure: 10Pa
Argon gas flow rate: 10 sccm
・ Oxygen gas flow rate: 30 sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.8kW
SiNC was placed in the film formation chamber of the plasma CVD apparatus, HMDSN was used as the source gas, and a gas barrier layer was provided so that the silicon oxide carbide film thickness was 100 nm under the following film formation conditions.
<Film formation conditions>
・ Film pressure: 10Pa
Argon gas flow rate: 10 sccm
・ Nitrogen gas flow rate: 20sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.2 kW

(Smoothing layer) Moreover, the formation method of the smoothing layer 17 of an Example , a reference example, and a comparative example is as follows.
As a sol-gel layer used as a smoothing layer, a coating agent mainly composed of aminoalkyltrialkoxysilane is applied by a spin coating method, heated at 120 ° C. for 2 minutes, and then dried at 160 ° C. with a dryer. It is dried for a time to form a 1 μm thick sol-gel layer (planarization layer).
As a UV curable resin layer used as a smoothing layer, a UV curable acrylate added with a photopolymerization initiator is applied, dried on a hot plate at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays (UV) using a high pressure mercury lamp. Irradiation and UV curing are performed to form a smoothing layer having a thickness of 2 μm.
As the cardo polymer layer used as the smoothing layer, a coating agent V-259-EH (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) mainly composed of cardo polymer is applied by a spin coating method and dried at 120 ° C. for 2 minutes. Further, it is dried with hot air at 160 ° C. for 60 minutes to form a smoothing layer having a thickness of 1 μm.

( Reference Example 1)
Each layer is formed under the above conditions, and a gas barrier film comprising a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first UV curable resin composition) Got.

( Reference example 2)
Each layer is formed under the above conditions, and a gas barrier film comprising a curable resin layer (second UV curable resin composition) / base film / curable resin layer (second UV curable resin composition) Got.

( Reference Example 3)
Each layer is formed under the above conditions, and a gas barrier film comprising a curable resin layer (third UV curable resin composition) / base film / curable resin layer (third UV curable resin composition) Got.

( Reference Example 4)
A gas barrier layer is formed on one side of the film obtained in Reference Example 1 under the conditions described above, and a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first A gas barrier film composed of (UV curable resin composition) / gas barrier layer (SiON) was obtained.

( Reference Example 5)
A gas barrier layer is formed on one side of the film obtained in Reference Example 2 under the conditions described above, and a curable resin layer (second UV curable resin composition) / base film / curable resin layer (second Gas curable resin composition) / gas barrier layer (SiOC) was obtained.

( Reference Example 6)
A gas barrier layer is formed on one side of the film obtained in Reference Example 3 under the conditions described above, and a curable resin layer (third UV curable resin composition) / base film / curable resin layer (third A gas barrier film comprising a UV curable resin composition) / gas barrier layer (SiNC) was obtained.

( Reference Example 7)
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 4 under the conditions described above, and a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first No. 1 UV curable resin composition) / gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) was obtained.

( Reference Example 8)
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 5 under the above-described conditions, and a curable resin layer (second UV curable resin composition) / base film / curable resin layer (first No. 2 UV curable resin composition) / gas barrier layer (SiOC) / smoothing layer ( UV curable resin layer ) was obtained.

( Reference Example 9)
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 6 under the conditions described above, and a curable resin layer (third UV curable resin composition) / base film / curable resin layer (first No. 3 UV curable resin composition) / gas barrier layer (SiNC) / smoothing layer ( UV curable resin layer ) was obtained.

(Example 10)
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 4 under the conditions described above, and a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first No. 1 UV curable resin composition) / gas barrier layer (SiON) / smoothing layer (cardo polymer) was obtained.

Example 11
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 5 under the above-described conditions, and a curable resin layer (second UV curable resin composition) / base film / curable resin layer (first No. 2 UV curable resin composition) / gas barrier layer (SiOC) / smoothing layer (cardo polymer) was obtained.

(Example 12)
A smoothing layer is formed on the gas barrier layer surface of the film obtained in Reference Example 6 under the conditions described above, and a curable resin layer (third UV curable resin composition) / base film / curable resin layer (first No. 3 UV curable resin composition) / gas barrier layer (SiNC) / smoothing layer (cardo polymer) was obtained.

( Reference Example 13)
A gas barrier layer is formed on the smoothing layer surface of the film obtained in Reference Example 7 under the above-described conditions, and a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first No. 1 UV curable resin composition) / gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) / gas barrier layer (SiON).

( Reference Example 14)
A gas barrier layer is formed on the smoothing layer surface of the film obtained in Reference Example 8 under the above-described conditions, and a curable resin layer (second UV curable resin composition) / base film / curable resin layer (first No. 2 UV curable resin composition) / gas barrier layer (SiOC) / smoothing layer ( UV curable resin layer ) / gas barrier layer (SiOC).

( Reference Example 15)
A gas barrier layer was formed on the smoothing layer surface of the film obtained in Reference Example 9 under the above-described conditions, and a curable resin layer (third UV curable resin composition) / base film / curable resin layer (first No. 3 UV curable resin composition) / gas barrier layer (SiNC) / smoothing layer ( UV curable resin layer ) / gas barrier layer (SiNC).

Example 16
A gas barrier layer was formed on the smoothing layer surface of the film obtained in Example 10 under the conditions described above, and a curable resin layer (first UV curable resin composition) / base film / curable resin layer (first No. 1 UV curable resin composition) / gas barrier layer (SiON) / smoothing layer (cardo polymer) gas barrier layer (SiOC) was obtained.

(Example 17)
A gas barrier layer was formed on the smoothing layer surface of the film obtained in Example 11 under the conditions described above, and a curable resin layer (second UV curable resin composition) / base film / curable resin layer (first No. 2 UV curable resin composition) / gas barrier layer (SiOC) / smoothing layer (cardo polymer) / gas barrier layer (SiOC).

(Example 18)
A gas barrier layer was formed on the smoothing layer surface of the film obtained in Example 12 under the conditions described above, and a curable resin layer (third UV curable resin composition) / base film / curable resin layer (first No. 3 UV curable resin composition) / gas barrier layer (SiNC) / smoothing layer (cardo polymer) / gas barrier layer (SiNC).

( Reference Example 19)
On the opposite side of the film obtained in Reference Example 13, a layer was formed under the above conditions so as to be symmetrical, and a gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) and a gas barrier layer (SiON) were cured. Mold resin layer (first UV curable resin composition) / base film / curable resin layer (first UV curable resin composition) / gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) / A gas barrier film comprising a gas barrier layer (SiON) was obtained.

( Reference Example 20)
A gas barrier film was obtained in the same manner as in Reference Example 19 except that the film obtained in Reference Example 14 was used.

( Reference Example 21)
A gas barrier film was obtained in the same manner as in Reference Example 19 except that the film obtained in Reference Example 15 was used.

(Example 22)
A gas barrier film was obtained in the same manner as in Reference Example 19 except that the film obtained in Example 16 was used.

(Example 23)
A gas barrier film was obtained in the same manner as in Reference Example 19 except that the film obtained in Example 17 was used.

(Example 24)
A gas barrier film was obtained in the same manner as in Reference Example 19 except that the film obtained in Example 18 was used.

( Reference Example 25)
A transparent electrode (indium zinc oxide) was entirely formed on the gas barrier layer (SiON) surface of the gas barrier film of Reference Example 19 by sputtering. On this indium zinc oxide, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), patterning is performed by a photolithographic method, and at a position corresponding to the fluorescence conversion layer of each color. A transparent electrode layer having a stripe pattern with a width of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm is formed, and a gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) / gas barrier layer (SiON) / Curable resin layer (first UV curable resin composition) / base film / curable resin layer (first UV curable resin composition) / gas barrier layer (SiON) / smoothing layer ( UV curable resin layer) ) / Gas barrier layer (SiON) / transparent electrode layer (ITO) to obtain a display substrate.
As a result of evaluating the characteristics of the obtained display substrate, the water vapor transmission rate is 0.01 g / m ² · day or less and the oxygen transmission rate is 0.01 cc / m ² · day · atm or less. And there was no significant growth or deflection.

(Example 26)
A display substrate was obtained in the same manner as in Reference Example 25 except that the gas barrier film of Example 22 was used.
As a result of evaluating the characteristics of the obtained display substrate, the water vapor transmission rate is 0.01 g / m ² · day or less and the oxygen transmission rate is 0.01 cc / m ² · day · atm or less. And there was no significant growth or deflection.

( Reference Example 27)
A liquid crystal display was manufactured using the gas barrier film of Reference Example 21 with a well-known technique and configuration, and the LCD display was continuously driven for 100 hours.

( Reference Example 28)
(1) A sheet (30 cm × 21 cm) polycarbonate (PC) film having a deflection temperature under load of 160 ° C. and a thickness of 200 μm was used as the substrate 11.
(2) Formation of blue color filter layer A blue filter material (Color Mosaic CB-7001: trade name, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied onto the polycarbonate (PC) film using a spin coating method. The coating film was patterned by a photolithographic method to form a blue color filter layer having a stripe pattern with a line width of 0.1 mm, a pitch (period) of 0.33 mm, and a film thickness of 6 μm.
(3) Formation of green conversion layer Coumarin 6 (0.7 parts by mass) as a fluorescent dye was dissolved in 120 parts by mass of propylene glycol monoethyl acetate (PEGMA) as a solvent. 100 parts by mass of “V259PA / P5” (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) as a photopolymerizable resin was added to the obtained solution and dissolved to obtain a coating solution.
On the transparent support substrate on which the blue color filter layer obtained in the above step is formed, the coating solution prepared as described above is applied using a spin coating method, patterned by a photolithographic method, and line width A green color conversion layer having a stripe pattern of 0.1 mm, a pitch (period) of 0.33 mm, and a film thickness of 10 μm was formed.
(4) Formation of red conversion layer As fluorescent dyes, coumarin 6 (0.6 parts by mass), rhodamine 6G (0.3 parts by mass), and basic violet 11 (0.3 parts by mass) were used as propylene glycol mono-monomers. It was dissolved in 120 parts by mass of ethyl acetate (PEGMA). 100 parts by mass of a photopolymerizable resin “V259PA / P5” (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) was added to the solution and dissolved to obtain a coating solution.
On the transparent support substrate on which the blue color filter layer and the green color conversion layer are formed, the coating solution prepared as described above is applied using a spin coating method, and patterned by a photolithographic method, with a line width of 0.1 mm, A red color conversion layer having a stripe pattern with a pitch (period) of 0.33 mm and a film thickness of 10 μm was formed.
The line-shaped patterns of the red color conversion layer, the green color conversion layer, and the blue color filter layer formed as described above are arranged in parallel with the gap width between them being 0.01 mm to form each color conversion layer.
(5) Formation of gas barrier layer and smoothing layer Each layer is sequentially formed on both surfaces of the base material including the color conversion layer formed in the above-described step in the same manner as in Reference Example 19 to obtain a gas barrier layer (SiON) / smoothing layer. ( UV curable resin layer ) / Gas barrier layer (SiON) / Curable resin layer (first UV curable resin composition) / Base film / Color filter layer / Curable resin layer (First UV curable resin composition) Product) / gas barrier layer (SiON) / smoothing layer ( UV cured resin layer ) / gas barrier layer (SiON).
(6) Formation of transparent electrode layer A transparent electrode (indium zinc oxide) was formed on the entire surface of the gas barrier layer (SiON) by sputtering. On this indium zinc oxide, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), patterning is performed by a photolithographic method, and at a position corresponding to the fluorescence conversion layer of each color. A transparent electrode layer having a stripe pattern with a width of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm was formed.
(7) Formation of organic EL related layer On the transparent electrode layer surface, a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer are sequentially formed on the entire surface without breaking the vacuum in a resistance heating vapor deposition apparatus. did. During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. As the hole injection layer, copper phthalocyanine (CuPc) was laminated so as to have a film thickness of 100 nm. As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (—NPD) was stacked so as to have a film thickness of 20 nm. As the organic light emitting layer, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) was laminated so as to have a film thickness of 30 nm. As the electron injection layer, aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated so as to have a film thickness of 20 nm.
Next, using a mask that can obtain a pattern with a width of 0.30 mm and an interval of 0.03 mm perpendicular to the stripe pattern of the anode (transparent electrode layer) without breaking the vacuum, a 200 nm thick Mg / Ag (mass) A cathode composed of 10/1 ratio layers was formed. The organic EL light-emitting device thus obtained was sealed with a sealing glass and a UV curable adhesive in a dry nitrogen atmosphere in a glove box (both oxygen and moisture concentrations were 10 ppm or less), and a gas barrier layer (SiON) / smooth Layer ( UV curable resin layer ) / gas barrier layer (SiON) / curable resin layer (first UV curable resin composition) / base film / color filter layer / curable resin layer (first UV curable type) Resin composition) / gas barrier layer (SiON) / smoothing layer ( UV curable resin layer ) / gas barrier layer (SiON) / transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode Thus, an organic EL color display having a layer structure of:
The organic EL color display was continuously driven for 100 hours, but could be displayed satisfactorily without problems.

  (Comparative example 1) Each layer is formed on said conditions, A curable resin layer (4th UV curable resin composition) / base film / curable resin layer (4th UV curable resin composition) A gas barrier film comprising:

  (Comparative example 2) Each layer is formed on said conditions, A curable resin layer (5th UV curable resin composition) / base film / curable resin layer (5th UV curable resin composition) A gas barrier film comprising:

(Comparative Example 3) A gas barrier was used in the same manner as in Reference Example 1 except that a polyethylene terephthalate (PET) resin film (manufactured by Toyobo Co., Ltd.) having a deflection temperature under load of 120 ° C. and a thickness of 200 μm was used as the substrate. A protective film was prepared.

(Evaluation) Evaluation is made by measuring the water vapor transmission rate and the oxygen transmission rate in the gas barrier film state and the organic EL element state by the following measurement method, and the results are shown in Table 1.
The water vapor transmission rate was measured using a water vapor transmission rate measurement device (manufactured by MOCON, USA, PERMAT RAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. The detection limit is 0.01 g / m ² · day, and when it is less than the detection limit, it is expressed as 0.01 g / m ² / day or less.
The oxygen permeability was measured using an oxygen gas permeability measuring device (manufactured by MOCON, USA, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% Rh. The detection limit is 0.01 cc / m ² · day · atm, and when it is less than the detection limit, it is expressed as 0.01 cc / m ² / day or less. Moreover, when it is more than the detection limit maximum, it represents by (-).
The measurement results are shown in Table 1.

(Evaluation Results) water vapor permeability of the gas barrier films of Reference Examples 1 to 3 30.8~32.0g / m ² · day, and the oxygen permeability Ru der least greatly limit of detection. The water vapor permeability of the gas barrier films of Reference Examples 4 to 6 was improved to 0.23 to 0.35 g / m ² · day and the oxygen permeability was 2.1 to 2.3 cc / m ² · day · atm . In Examples 10 to 12, 16 to 18, 22 to 24, and Reference Examples 7 to 9, 13 to 15, and 19 to 21, the water vapor transmission rate is 0.01 g / m ² · day or less, and the oxygen transmission rate is also 0.1 . The gas barrier property was not more than 01 cc / m ² · day · atm, and there was no significant elongation or deflection.
As a result of evaluating the characteristics of the gas barrier films of Comparative Examples 1 to 3, the water vapor transmission rate was 31.3 to 31.7 g / m ² · day, the oxygen transmission rate was largely above the detection limit, and used as a display substrate. It was not possible level.
All the light transmittances were good.

It is sectional drawing which shows one Example of the gas barrier film of this invention. It is sectional drawing which shows one Example of the board | substrate for displays of this invention.

10: gas barrier film 11: substrate 12A, 12B: curable resin layer 13A, 13B: first gas barrier layer 15A, 15B: first smoothing layer 17A, 17B: second gas barrier layer 19A, 19B: second smoothing Layer 20: Display substrate 21: Receiving layer

Claims (12)

A gas barrier film comprising a curable resin layer on both surfaces of a base material, a first gas barrier layer on at least one side of the curable resin layer surface, and a first smoothing layer on at least one side of the first gas barrier layer surface. The material is a resin having a deflection temperature under load of 150 ° C. or more, the linear expansion coefficient of the curable resin layer is 100 ppm / K or less, and the refractive index difference n between the substrate and the curable resin is 0.03 ≦ n. ≦ 0.18, and the gas barrier layer is any one selected from the group consisting of inorganic oxide, inorganic oxynitride, inorganic oxycarbide and inorganic oxynitride carbide, and the smoothing layer is a cardo polymer A silane coupling agent having an organic functional group and a hydrolyzable group, and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent Gas barrier film characterized in that a layer, which contains at least coating a is a layer configuration paint composition as a raw material, or an epoxy backbone polymer. The gas barrier film according to claim 1, wherein a second gas barrier layer is provided on at least one side of the first smoothing layer surface. The gas barrier film according to claim 2, wherein a second smoothing layer is provided on at least one side of the second gas barrier layer surface. The gas barrier film according to any one of claims 1 to 3 , wherein the substrate is a linear polymer aromatic polycarbonate having a carbonate ester skeleton having a deflection temperature under load of 160 ° C or higher. The gas barrier film according to any one of claims 1 to 4 , wherein the curable resin layer is an ionizing radiation curable resin. The gas barrier according to any one of claims 2 to 5 , wherein the second gas barrier layer is selected from the group consisting of an inorganic oxide, an inorganic oxynitride, an inorganic oxycarbide, and an inorganic oxynitride carbide. Sex film. The second smoothing layer is a layer containing a cardo polymer, a layer containing an acrylic skeleton polymer, a silane coupling agent having an organic functional group and a hydrolyzable group, and an organic that reacts with the organic functional group of the silane coupling agent. The layer according to any one of claims 4 to 6, which is a layer which is a coating film of a coating composition composed of at least a crosslinkable compound having a functional group as a raw material, or a layer containing an epoxy skeleton polymer. The gas barrier film according to the description. A display substrate comprising the gas barrier film according to claim 1. A display substrate, wherein a transparent conductive film is formed on a gas barrier layer or a smoothing layer surface of the gas barrier film according to claim 1. A display comprising the display substrate according to claim 8. A liquid crystal display device comprising the display substrate according to claim 8. An organic EL device comprising the display substrate according to claim 8.

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