JP2005096108A - Antireflection gas barrier substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection gas barrier substrate having an antireflection function for suppressing the reflection of light to be enhanced in total light transmissivity and gas barrier properties. <P>SOLUTION: The antireflection gas barrier substrate has a base material, the first inorganic film formed on the base material, the organic film formed on the first inorganic film and the second inorganic film formed on the organic film and is characterized in that the luminous reflectance in a visible region is 20% or below, the total light transmissivity is 80% or above, oxygen permeability is 0.5 cc/m<SP>2</SP>day or below and steam permeability is 0.5 g/m<SP>2</SP>day or below. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antireflection gas barrier substrate having a high gas barrier property and an antireflection function, which is used for display substrates such as organic EL devices and liquid crystal display devices.

  In recent years, with the diversification of information, display devices in the information field have high brightness, high contrast, high luminous efficiency, high resolution, wide viewing angle, miniaturization, colorization, lightness, thinness. Such excellent features as a display device are demanded, and active development is progressing toward further low power consumption and high-speed response. Particularly, high-definition full-color display devices have been widely devised.

  What is important for practical application as such a color display device is that it has a fine color display function and has long-term stability. However, some display devices have a drawback in that light emission characteristics such as current-luminance characteristics are remarkably deteriorated when driven for a certain period.

  A typical cause of the deterioration of the light emission characteristics is the growth of light emission defect points called dark spots. This dark spot is considered to be caused by oxidation or aggregation of the laminated constituent material of the display device due to oxygen or moisture in the display device. The growth of the dark spot proceeds not only during energization (during driving) but also during storage, and in an extreme case spreads over the entire light emitting surface. The growth is particularly accelerated by (1) oxygen or moisture present around the display device, (2) affected by oxygen or moisture present as an adsorbate in the organic laminate film, and (3) display device manufacture. It is considered that it is also affected by moisture adsorbed on parts used at times, or moisture intrusion during production.

As a technique for preventing the moisture from entering the display device, for example, as an organic EL element manufacturing method, an insulating inorganic oxide film layer is provided on the organic EL layer (Patent Document 1). Further, it is disclosed that an overcoat layer and an insulating inorganic oxide film layer are provided on the organic EL layer (Patent Document 2). The inorganic oxide film layer is required to have high moisture resistance for maintaining the life of the organic EL element, and the gas permeability coefficient of water vapor or oxygen in the inorganic oxide film layer is measured by the gas permeability test method of JIS K7126. Is preferably 10 ⁻¹³ cc · cm / cm ₂ · s · cmHg or less.

Further, as shown in Patent Document 3 and Patent Document 4, as a method for producing a color filter, there is a method of forming SiO _x and SiN _x by DC sputtering on a resin protective layer formed on the color filter layer. This method has the effect of improving the adhesion of the transparent conductive film. Further, a method of sintering low melting point glass is known (Patent Document 5). In addition, as a sealing method for blocking the organic EL element from the outside air, a method of forming a SiN _X film by a CVD method is known (Patent Document 6).

  However, in any of the inventions described in any of the above-mentioned documents, it can be said that the moisture-proof property and gas barrier property for preventing deterioration of a display device such as an organic EL element are not sufficient.

  Thus, gas barrier films in which inorganic layers and organic layers are alternately stacked on an organic EL layer are disclosed (see, for example, Patent Document 7, Patent Document 8, and Patent Document 9). When such a gas barrier film is a laminate composed of, for example, an inorganic layer, an organic layer, and an inorganic layer, pinholes in the first inorganic layer formed on the organic EL layer are formed. It is buried by forming an organic layer thereon, and further, an inorganic layer is formed on the organic layer, thereby preventing entry of oxygen, moisture and the like.

  Conventionally, a substrate using a glass substrate is known as a support substrate for a display element such as an organic EL element or a liquid crystal display element. However, the glass substrate has a drawback that it is heavy, hard and easily broken. Therefore, Patent Document 10 discloses the use of a plastic substrate instead of a glass substrate from the viewpoint of increasing the size, weight, and impact resistance of the display element. However, while the plastic substrate is light and flexible and difficult to break, the gas barrier property is poor as compared with the glass substrate, and it has been difficult to maintain the performance of the display element for a long time.

  On the other hand, in order to improve the gas barrier property of the plastic substrate, it is only necessary to laminate an inorganic layer and an organic layer in the gas barrier film. However, when these layers are laminated, the reflection of light increases and the transmittance decreases. Therefore, there is a problem that the luminance of the display element is lowered.

  Therefore, Patent Document 11 discloses a gas barrier film in which inorganic layers and organic layers are alternately stacked, and by setting the film thickness of the inorganic layer to λ / 2 or λ / 4 with respect to the design wavelength λ, A method for preventing reflection at the interface between the inorganic layer and the organic layer and suppressing reduction in the transmittance of the gas barrier film is disclosed. However, the gas barrier property of the gas barrier film is not described.

JP-A-8-279394 JP 2002-318543 A Japanese Patent Laid-Open No. 7-146480 Japanese Patent Laid-Open No. 10-10518 JP 2000-214318 A JP 2000-223264 A JP 2003-53873 A JP 2002-1000046 A JP 2002-18994 A Japanese Patent Laid-Open No. 2001-150584 Japanese Patent Laid-Open No. 2002-40205

  The present invention has been made in view of the above problems, and provides an antireflection gas barrier substrate having a high total light transmittance and a high gas barrier property by having an antireflection function for suppressing light reflection. Is the main purpose.

In order to achieve the above object, the present invention provides a base material, a first inorganic film formed on the base material, an organic film formed on the first inorganic film, and formed on the organic film. A luminous reflectance in the visible light region is 20% or less, a total light transmittance is 80% or more, an oxygen transmittance is 0.5 cc / m ² · day or less, water vapor Provided is an antireflection gas barrier substrate characterized by having a transmittance of 0.5 g / m ² · day or less.

  When the luminous reflectance, total light transmittance, oxygen transmittance, and water vapor transmittance of the antireflection gas barrier substrate of the present invention are in the above-described ranges, the antireflection gas barrier substrate of the present invention is applied to, for example, an organic EL device. When used, it is possible to obtain a good image display free from defects such as dark spots because the luminous reflectance is high because the luminous reflectance is low and the gas barrier property is good.

  In the present invention, the optical thickness (film thickness × refractive index) of the first inorganic film is in the range of 140 nm to 1000 nm, and the optical film thickness (film thickness × refractive index) of the second inorganic film is It is preferably within the range of 10 nm to 1000 nm. When the optical film thickness (film thickness × refractive index) of the first inorganic film and the second inorganic film is within the above range, reflection on the antireflection gas barrier substrate can be suppressed, and the total light transmittance is It is because it can suppress that it falls.

  Moreover, in the said invention, it is preferable that the film thickness of the said 1st inorganic film exists in the range of 80 nm-500 nm, and the film thickness of the said 2nd inorganic film exists in the range of 10 nm-500 nm. Furthermore, it is preferable that the refractive index of the said 1st inorganic film and the said 2nd inorganic film exists in the range of 1.2-2.0. Similarly, in this case, since the film thickness and refractive index of the first inorganic film and the second inorganic film are within the above range, reflection on the antireflection gas barrier substrate can be suppressed, and the total light transmittance can be reduced. It is because it can suppress that it falls.

  Furthermore, in the present invention, the first inorganic film and the second inorganic film are preferably a silicon oxide film or a silicon oxynitride film. Since the silicon oxide film and the silicon oxynitride film have good adhesion to the organic film, the organic film effectively fills the pinhole even when the silicon oxide film or the silicon oxynitride film has a pinhole. This is because the gas barrier property can be increased.

  In the present invention, the organic film preferably has a cardo polymer. This is because when the organic film has a cardo polymer, the adhesion with the inorganic film is improved and the gas barrier property can be increased.

  Furthermore, in the present invention, the deposited film and the organic film are laminated in this order within the range of 2 to 6 layers on the organic film, and the uppermost layer is the second inorganic film. Good.

  Moreover, in this invention, it is preferable that the stress relaxation layer which relieve | moderates the stress concerning the said base material is formed in the surface on the opposite side to the surface in which the said 1st inorganic film | membrane was formed in the said base material. As a result, the stress generated when the first inorganic film, the organic film, and the second inorganic film are formed can be reduced, and warpage of the antireflection gas barrier substrate can be prevented. It is.

  The present invention also provides a display substrate using the antireflection gas barrier substrate. According to the present invention, by using the above-mentioned antireflection gas barrier substrate, since it has an antireflection function, it can be a display substrate having a high total light transmittance and a high gas barrier property, and used for various applications. It becomes possible.

  Moreover, in the said invention, it is preferable that the stress relaxation layer in the said antireflection gas barrier property board | substrate is a transparent conductive layer. This is because by forming a transparent conductive layer as the stress relaxation layer, the layer configuration can be simplified, and a display substrate can be efficiently produced.

  The present invention also provides a liquid crystal display element comprising the display substrate. According to the present invention, the display substrate is not affected by oxygen, water vapor, or the like even over time, so that the display quality is not deteriorated and the antireflection function is provided, so that a high brightness image display is achieved. Can be obtained.

  Furthermore, this invention provides the organic EL element characterized by having the said board | substrate for a display. According to the present invention, by having the display substrate, there is no defect such as a dark spot because it is not affected by oxygen or water vapor even over time, and since it has an antireflection function, a high brightness image display is possible. It can be set as the obtained organic EL element.

  According to the present invention, since the antireflection gas barrier substrate has excellent antireflection properties and gas barrier properties, when the antireflection gas barrier substrate of the present invention is used in, for example, an organic EL device, defects such as dark spots are present. Therefore, it is possible to obtain a high-quality organic EL element that can display an image with high luminance.

  The present invention includes an antireflection gas barrier substrate, a display substrate using the same, a liquid crystal display element, and an organic EL element. Hereinafter, each will be described in detail.

A. Antireflection Gas Barrier Substrate First, the antireflection gas barrier substrate of the present invention will be described.

The antireflection gas barrier substrate of the present invention is formed on a base material, a first inorganic film formed on the base material, an organic film formed on the first inorganic film, and the organic film. And a second inorganic film, the luminous reflectance in the visible light region is 20% or less, the total light transmittance is 80% or more, the oxygen transmission rate is 0.5 cc / m ² · day or less, the water vapor transmission rate Is 0.5 g / m ² · day or less.

  The antireflection gas barrier substrate of the present invention will be described with reference to the drawings. FIG. 1 shows an example of an antireflection gas barrier substrate of the present invention. As shown in FIG. 1, the antireflective gas barrier substrate of the present invention includes a base material 1, a first inorganic film 2 formed on the base material 1, and an organic formed on the first inorganic film 2. The film 3 and the second inorganic film 4 formed on the organic film 3 are included.

  According to the present invention, the first inorganic film, the organic film, and the second inorganic film are sequentially stacked, so that the organic film is formed on the first inorganic film even when pinholes exist in the first inorganic film. This pinhole is filled, and further, by forming a second inorganic film on the organic film, the generation of pinholes penetrating from the first inorganic film to the surface of the second inorganic film can be suppressed, It becomes possible to prevent entry of oxygen, water vapor, and the like.

  In addition, in the present invention, there is a problem in that the light transmittance is reduced because light reflection occurs at the interface of each layer by laminating multiple layers in order to improve the gas barrier property. When the luminous reflectance is in the above-described range, the reflection of light on the antireflection gas barrier substrate can be suppressed, and the reduction of the total light transmittance can be suppressed.

  Therefore, when an anti-reflection gas barrier substrate of the present invention is used, for example, as an organic EL element, a high-luminance image display is possible because there is no defect such as a dark spot because the gas barrier property is high and the luminous reflectance is low. Can be obtained.

  In the present invention, the luminous reflectance in the visible light region of the antireflection gas barrier substrate is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less. When the luminous reflectance of the antireflection gas barrier substrate of the present invention is in the above-described range, reflection of light on the antireflection gas barrier substrate can be suppressed, and a decrease in total light transmittance can be suppressed. Therefore, when the antireflection gas barrier substrate of the present invention is used for an organic EL element, for example, it is possible to obtain a high-luminance image display.

  In the present invention, the total light transmittance in the visible light region of the antireflection gas barrier substrate is preferably 80% or more, and more preferably 85% or more. Since the total light transmittance of the antireflective gas barrier substrate of the present invention is in the above-described range, when the antireflective gas barrier substrate of the present invention is used for an organic EL element, for example, a high-luminance image display can be obtained. This is because it becomes possible.

  In addition, the said luminous reflectance and the said total light transmittance are the average values of the value measured using Shimadzu Corporation Corp. UV-3100 within the wavelength range of 380 nm-800 nm.

In the present invention, the oxygen permeability in the antireflection gas barrier substrate, 0.5cc ^/ m 2 · day or less, preferably 0.1cc ^/ m 2 · day or less, or less particularly 0.05cc ^/ m 2 · day preferably, the water vapor transmission rate, 0.5g ^/ m 2 · day or less, preferably 0.1g ^/ m 2 · day or less, and preferably less especially 0.05g ^/ m 2 · day. When the oxygen permeability and water vapor permeability of the antireflective gas barrier substrate of the present invention are within the above-described ranges, the gas barrier property can be made high, and for example, a liquid crystal having a member weak against oxygen, water vapor, or the like. This is because it can be used for a support substrate such as a display element or an organic EL element.

  Here, the oxygen permeability is a value measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% Rh. The water vapor transmission rate was measured using a water vapor transmission rate measurement device (manufactured by MOCON, PERMATRAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. Value.

  Hereinafter, each structure of such an antireflection gas barrier substrate will be described.

1. Base Material First, the base material used for the antireflection gas barrier substrate of the present invention will be described. The substrate used in the present invention is not particularly limited as long as the first inorganic film described later can be formed on the substrate, but in the present invention, the transparent group is transparent to visible light. A material is preferred. This is because the antireflection gas barrier substrate of the present invention can be used for a display substrate, for example. In the present invention, for example, a glass plate or a film or sheet formed of an organic material can be used as such a transparent substrate.

  When a glass plate is used as the transparent substrate in the present invention, it is not particularly limited as long as it is highly permeable to visible light, and may be a raw glass plate, for example. Moreover, the processed glass plate etc. may be sufficient. As such a glass plate, both alkali glass and non-alkali glass can be used. However, when impurities are a problem in the antireflection gas barrier substrate of the present invention, for example, Pyrex (registered trademark) glass or the like. It is preferable to use non-alkali glass. The type of the processed glass plate is appropriately selected according to the application of the antireflection gas barrier substrate of the present invention. For example, the processed glass plate is coated on a transparent glass substrate or has a step process. Etc.

  The film thickness of such a glass plate is preferably within a range of 30 μm to 2 mm, and in particular, when used as a flexible substrate, within a range of 30 μm to 1 mm, particularly within a range of 30 μm to 0.5 mm. Is preferable, and when used as a rigid substrate, it is preferably within a range of 60 μm to 2 mm.

  The organic material used as the transparent substrate in the present invention includes polyarylate resin, polycarbonate resin, crystallized polyethylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, UV curable methacrylic resin, polyether sulfone resin, poly Examples include ether ether ketone resins, polyether imide resins, polyphenylene sulfide resins, and polyimide resins.

  Here, in the present invention, when the antireflection gas barrier substrate is used for, for example, a liquid crystal display element or an organic EL element, it is preferable to have heat resistance, and as such an organic material having heat resistance, Examples include polar polymers having a cycloalkyl skeleton. Specific examples include acrylate compounds or methacrylate compounds having a cycloalkyl skeleton and derivatives thereof. Among them, a resin composition containing a (meth) acrylate compound having a cycloalkyl skeleton as shown in JP-A-11-222508 (meaning an acrylate compound or a methacrylate compound in the present invention) and a derivative thereof. Can be mentioned.

  In this case, the organic material having heat resistance does not exhibit a glass transition point (Tg), has a linear expansion coefficient of 80 ppm or less, and a total light transmittance of 85% or more within a range from room temperature to 150 ° C. Preferably there is. If the linear expansion coefficient exceeds the above range, the substrate dimensions are not stable at high temperatures, and it is likely to cause inconvenience that the barrier performance deteriorates due to thermal expansion and contraction, or that the thermal process cannot withstand. It is. Therefore, when manufacturing a liquid crystal display element, an organic EL element, etc., it may be exposed to a process at about 200 ° C. However, since the base material has the above-described characteristics, the antireflection gas barrier substrate of the present invention is used. Can be used to stably produce a liquid crystal display element, an organic EL element or the like.

  Here, the linear expansion coefficient means that a sample having a width of 5 mm and a length of 20 mm is used, a constant load (2 g) is applied in the length direction, and the temperature range from 25 to 200 ° C. is increased at a rate of temperature increase of 5 ° C./min. Let us say the amount of dimensional variation measured. Moreover, the said total light transmittance is the value measured by the test method JISK7361-1 of the total light transmittance using the Nippon Denshoku Industries Co., Ltd. total light transmittance measuring apparatus.

  In addition, the base material used in the present invention includes the above-described organic material, for example, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin). ), Poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, fluorine resins, acetal resins, cellulose resins , Polyether sulfone resin and the like can be used in combination of two or more.

  In the present invention, a method of forming a substrate using the organic material as described above is, for example, using one or more of the above-mentioned various resins, and an extrusion method, a cast molding method, a T-die method, a cutting method. , A method of forming the above-mentioned various resins alone using an inflation method or other film-forming methods, or a method of forming a multilayer co-extrusion film using two or more types of resins. Furthermore, there may be mentioned a method of using two or more kinds of resins and mixing them before forming a film to form a film. In addition, a resin film or sheet of each layer is manufactured by these film forming methods, and in addition, when stretching is required, for example, a tenter method or a tubular method is used to make a uniaxial or two-axial film. Various resin films or sheets formed by stretching in the axial direction can be used. Also, the above-mentioned various resin films or sheets can be bonded together.

  In addition, when one or more of the above-mentioned various resins are used and the film is formed, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying the releasability, flame retardancy, antifungal property, electrical properties, strength and the like. The addition amount can be arbitrarily added from a very small amount to several tens of percent depending on the purpose. In the above, as a general additive, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Also, an improving resin or the like can be used.

  In the present invention, when using the organic material as described above as a base material, it is preferably in the range of 10 μm to 500 μm, more preferably in the range of 50 to 400 μm, and particularly preferably in the range of 100 to 300 μm. When the film thickness is thicker than the above range, the impact resistance is inferior when processing the antireflection gas barrier substrate of the present invention, and winding becomes difficult during winding, and the gas barrier property against water vapor, oxygen, etc. deteriorates. This is because there is a case where it is seen. Further, when the film thickness is thinner than the above range, the mechanical suitability is poor, and the gas barrier property against water vapor, oxygen and the like is lowered.

  Moreover, in this invention, when using the material which does not have heat resistance mentioned above as a base material, when using a glass plate, etc., the transparent resin layer which has heat resistance can be formed on the base material. preferable. Furthermore, the transparent resin layer having such heat resistance does not exhibit a glass transition point (Tg), has a linear expansion coefficient of 80 ppm or less in a range from room temperature to 150 ° C., and has a total light transmittance of 85%. The above is preferable. This is because heat resistance can be imparted to the base material.

  Such a transparent resin layer is preferably a polar polymer having a cycloalkyl skeleton, which is an organic material having heat resistance as described above. Specifically, such a material is preferably a polar (meth) acrylate compound or a derivative thereof, for example, methyl (meth) acrylate homopolymer or methyl (meth) acrylate and other Examples include a copolymer obtained by polymerizing a mixture of monomers having a copolymerizable vinyl group (in the present invention, (meth) acryl means acryl or methacryl). Examples of the monomer copolymerizable with methyl (meth) acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and 2,2,2-trifluoro. Acrylic esters such as ethyl acrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methacrylic esters such as 2,2,2-trifluoroethyl methacrylate, vinyl compounds such as acrylonitrile and styrene, maleic anhydride, itaconic anhydride And maleimide compounds such as cyclohexylmaleimide and phenylmaleimide.

  In the present invention, the transparent resin layer is mixed with the resin and additives such as a polymerization initiator and a polyfunctional acrylate monomer, if necessary, and applied to the transparent substrate or glass substrate, and then cured by ultraviolet irradiation. Can be formed.

  The film thickness of such a transparent resin layer is desirably 5 nm to 100 μm, and the film thickness of the transparent resin layer is within a range of 0.00001 to 1 when the film thickness of the substrate described above is 1. Preferably there is.

  In addition, when the antireflection gas barrier substrate of the present invention is used as a display substrate used for a liquid crystal display element, an organic EL element, or the like, the heat resistance of the substrate is 150 ° C. or higher, particularly 200 ° C. or higher, particularly 250. It is preferable to achieve a temperature of ° C or higher.

2. First Inorganic Film Next, the first inorganic film used in the present invention will be described. In the present invention, the first inorganic film is formed on the substrate, and has a film thickness and a refractive index that suppress reflection of light on the antireflection gas barrier substrate. In the present invention, by controlling the film thickness and refractive index of the first inorganic film and the second inorganic film described later, the reflection of light on the antireflection gas barrier substrate can be suppressed. It becomes possible to suppress the reduction of the total light transmittance by laminating the first inorganic film, the organic film, and the second inorganic film. Therefore, when the antireflection gas barrier substrate of the present invention is used, for example, as an organic EL element, it is possible to obtain a high luminance image display with high total light transmittance.

  In the present invention, the optical film thickness (film thickness × refractive index) of the first inorganic film is preferably 140 nm to 1000 nm, more preferably 140 nm to 500 nm, and particularly preferably 150 nm to 300 nm. When the optical film thickness (film thickness × refractive index) of the first inorganic film is within the above-described range, reflection on the antireflection gas barrier substrate can be suppressed, and the total light transmittance is reduced. It is because it can suppress.

  In the present invention, the optical film thickness means a value obtained by multiplying the film thickness and the refractive index. For example, when an optical film thickness that suppresses reflection on the antireflection gas barrier substrate is used, the film thickness is increased if a material having a low refractive index is used, and the film thickness is decreased if a material having a high refractive index is used.

  Here, the film thickness and refractive index of the first inorganic film are values measured using a spectroscopic ellipsometer (model number: UVISEL) manufactured by JOBIN YVON.

  In the present invention, the optical thickness (film thickness × refractive index) of the first inorganic film is not less than λ / 4 with respect to the wavelength λ of light incident on the antireflective gas barrier substrate, and in particular, λ / It is preferably 3 or more. When the optical film thickness (film thickness × refractive index) of the first inorganic film is within the above range, reflection on the antireflection gas barrier substrate can be effectively suppressed, and the total light transmittance is reduced. This is because this can be suppressed.

  Furthermore, in the present invention, the thickness of the first inorganic film is preferably in the range of 80 nm to 500 nm, particularly 80 nm to 300 nm, particularly 80 nm to 150 nm. This is because, when the film thickness of the first inorganic film is within the above-described range, reflection on the antireflection gas barrier substrate can be suppressed, and a decrease in total light transmittance can be suppressed. . In addition, if the thickness of the first inorganic film is thinner than the above-described range, the gas barrier property against water vapor, oxygen, or the like may be lowered, and the thickness of the first inorganic film is less than the above-described range. In the case of being thick, for example, when the antireflection gas barrier substrate of the present invention is produced, cracks or the like may be generated, and this causes deterioration of gas barrier properties against water vapor, oxygen gas, and the like.

  The refractive index of the first inorganic film is preferably 1.2 to 2.0, more preferably 1.7 to 2.0, and particularly preferably 1.8 to 2.0. In the present invention, as described above, by controlling the film thickness and refractive index of the first inorganic film, it is possible to effectively suppress the reflection of light on the antireflection gas barrier substrate.

  As described above, the first inorganic film used in the present invention has an effect of preventing reflection from the outside and preventing reflection of light, and also has an effect of blocking permeation of water vapor and oxygen. Therefore, it is preferable that the first inorganic film has electrical insulation, has barrier properties against gases and organic solvents, and has high transparency in the visible light region. As specific transparency, the total light transmittance in the visible light region is preferably 80% or more, more preferably 85% or more. Thereby, when the antireflection gas barrier substrate of the present invention is used for an organic EL element, an image display with high brightness can be obtained. Here, the said total light transmittance is the value measured by the test method JIS K7361-1 of the total light transmittance using the Nippon Denshoku Industries Co., Ltd. total light transmittance measuring apparatus.

  The material of the first inorganic film is not particularly limited as long as it has the above-described properties, but the transparent inorganic oxide film, the transparent inorganic oxynitride film, the transparent inorganic nitride film, or the transparent It is preferable to use one or a combination of two or more metal films. Moreover, as a metal contained in a 1st inorganic film | membrane, it is preferable that they are silicon, aluminum, magnesium, titanium, tin, indium, and cerium, and may contain 1 type, or 2 or more types. The transparent inorganic oxide film is preferably a silicon oxide film, a silicon oxynitride film, an aluminum oxide film, a magnesium oxide film, a titanium oxide film, a tin oxide film, or an indium oxide alloy film. The transparent inorganic nitride film is preferably a silicon nitride film, an aluminum nitride film, or a titanium nitride film. Further, the transparent metal film is preferably an aluminum film, a silver film, a tin film, a chromium film, a nickel film, or a titanium film.

  In the present invention, among the above materials, a silicon oxide film or a silicon oxynitride film is particularly preferable. This is because these films have good adhesion to an organic film described later.

  Moreover, in this invention, in order to improve gas barrier property, you may laminate | stack two or more layers of said inorganic film, The combination does not ask | require the same kind or a different kind.

  The formation of the first inorganic film is not particularly limited as long as it is performed by a vapor deposition method. Specifically, a vacuum vapor deposition method in which inorganic oxide, inorganic nitride, inorganic oxynitride or metal is used as a raw material and heated and vapor-deposited on a substrate; inorganic oxide, inorganic nitride, inorganic oxynitride or An oxidation reaction vapor deposition method in which metal is used as a raw material, is oxidized by introducing oxygen gas, and is deposited on a substrate; inorganic oxide, inorganic nitride, inorganic oxynitride or metal is used as a target raw material, and argon gas A sputtering method in which oxygen gas is introduced and sputtering is performed to deposit on a substrate; the substrate is heated by a plasma beam generated by a plasma gun on an inorganic oxide, inorganic nitride, inorganic oxynitride or metal; Physical vapor deposition (physical vapor deposition), such as ion plating, which is deposited on the material, and vapor deposition of silicon oxide. In the case of depositing a film, a plasma chemical vapor deposition method (Chemical Vapor Deposition method) using an organosilicon compound as a raw material can be used.

  In the present invention, as described above, it is preferable that the first inorganic film is a silicon oxide film or a silicon oxynitride film. Such a silicon oxide film uses an organosilicon compound as a raw material and is a low-temperature plasma chemical vapor. It can be formed using a phase growth method. Specific examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propylsilane. , Phenylsilane, vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like. Among the organosilicon compounds, tetramethoxysilane (TMOS) and hexamethyldisiloxane (HMDSO) are preferably used. This is because these are excellent in handleability and vapor deposition film characteristics.

3. Second Inorganic Film Next, the second inorganic film used in the present invention will be described. In this invention, a 2nd inorganic film | membrane is formed on the organic film mentioned later, and has a film thickness and refractive index which suppress reflection of the light in an antireflection gas barrier property board | substrate. In the present invention, as described above, by controlling the film thickness and refractive index of the first inorganic film and the second inorganic film, reflection of light on the antireflection gas barrier substrate can be suppressed, and total light transmission is achieved. It becomes possible to suppress the reduction of the rate. Therefore, when the antireflection gas barrier substrate of the present invention is used, for example, as an organic EL element, it is possible to obtain a high luminance image display with high total light transmittance.

  In the present invention, the optical thickness (film thickness × refractive index) of the second inorganic film is preferably in the range of 10 nm to 1000 nm, particularly 10 nm to 200 nm. When the film thickness and refractive index of the second inorganic film are within the above-described ranges, reflection on the antireflection gas barrier substrate can be suppressed, and reduction in total light transmittance can be suppressed. Because.

  In the present invention, the thickness of the second inorganic film is preferably 10 nm to 500 nm, more preferably 10 nm to 300 nm, particularly preferably 10 nm to 150 nm. This is because when the film thickness of the second inorganic film is within the above-described range, reflection on the antireflection gas barrier substrate can be suppressed, and a decrease in total light transmittance can be suppressed. . In addition, if the thickness of the second inorganic film is thinner than the above-described range, the gas barrier property against water vapor, oxygen and the like may be lowered, and the thickness of the second inorganic film is less than the above-described range. In the case where the thickness is too thick, for example, when the antireflection gas barrier substrate of the present invention is produced, cracks or the like may occur, and this causes deterioration of gas barrier properties against water vapor, oxygen gas and the like.

  As such a second inorganic film, like the first inorganic film, it has an action of preventing reflection from outside, preventing reflection of light, and also having an action of blocking permeation of water vapor and oxygen. It is. Therefore, as described in the column of the first inorganic film, it is preferable that the gas barrier property and the transparency to visible light are high. Further, when the antireflection gas barrier substrate of the present invention is used as a display substrate, a transparent conductive layer may be formed on the second inorganic film. In such a case, the second inorganic film is It is preferable to have a hardness that can withstand the force applied during the formation of the transparent conductive layer. Specifically, it is preferable to have a hardness of 2H or more according to the pencil hardness test JIS K5400.

  Since the other points of the second inorganic film are the same as those described in “2. First inorganic film” described above, description thereof is omitted here.

4). Next, the organic film used in the present invention will be described. In the present invention, the organic film is formed between the first inorganic film and the second inorganic film, and is a film having an organic substance.

  According to the present invention, the first inorganic film, the organic film, and the second inorganic film are sequentially laminated, so that even when a pinhole is present in the first inorganic film, the organic film is formed on the first inorganic film. This pinhole is filled by forming a second inorganic film on the organic film, thereby suppressing the generation of pinholes penetrating from the first inorganic film to the surface of the second inorganic film. It is possible to prevent entry of oxygen, water vapor and the like.

  Such an organic film is not particularly limited as long as it is a material capable of filling the pinholes of the first inorganic film and the second inorganic film, and is in close contact with the first inorganic film and the second inorganic film. Any material having good properties and capable of forming a flat film may be used. Thereby, the second inorganic film can be densely and flatly formed on the organic film, and the gas barrier property can be improved.

  Specific examples of the forming material include a thermosetting resin, a photocurable resin, a photothermal combination type curable resin, and a metal alkoxide.

  As the thermosetting resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea copolymer resin, etc. are used. be able to. These thermosetting resins are used by adding a curing agent such as a crosslinking agent or a polymerization initiator, a polymerization accelerator, or the like, if necessary.

  The resin composition containing the photocurable or photothermal combination type curable resin comprises (i) an acrylic polyfunctional monomer and oligomer having a plurality of acroyl groups and methacryloyl groups, and a photo or thermal polymerization initiator. Resin composition, (ii) Resin composition comprising polyvinylcinnamic acid ester and sensitizer, (iii) Resin composition comprising chain or cyclic olefin and bisazide, and (iv) Monomer having epoxy group and acid Examples thereof include a resin composition comprising a generator. In particular, a resin composition comprising (i) an acrylic polyfunctional monomer and oligomer and light or a thermal polymerization initiator is preferred because of high reliability such as solvent resistance and heat resistance. By making light and / or heat act on said resin composition, photocurable or photothermal combined use type curable resin is formed. Moreover, when using photocurable combined use curable resin, it is preferable that an average molecular weight is 3000 or more from the point which can make a softening point 45 degreeC or more.

  Furthermore, examples of the metal element of the metal alkoxide include Si, Al, Sr, Ba, Pb, Ti, Zr, La, and Na. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, trimethoxymethylsilane, dimethyldiethoxysilane, [2- (3-cyclohexenyl) ethyl] trimethoxysilane , [2- (3-cyclohexenyl) ethyl] triethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, (3-cyclopentadienylpropyl) triethoxysilane, cyclopentyltrimethoxysilane, etc. Alkoxysilane compounds; zirconium alkoxide compounds such as tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium; Titanium, may be mentioned tetraethoxy titanium, tetraisopropoxy titanium, titanium alkoxide compounds such as tetra butoxy titanium. These metal alkoxides can be used alone or in combination of two or more. As said metal alkoxide, it is preferable to use an alkoxysilane compound especially from points, such as the handleability, hardening reactivity, economical efficiency, etc.

  Moreover, a silane coupling agent can be added to the said alkoxysilane compound as a crosslinking agent etc. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyl silicone Also Can be used in combination of two or more. As the amount of use, it is only necessary to add a trace amount.

  Such metal alkoxides undergo hydrolysis and polycondensation reactions in the presence of water or alcohol, or by adding an organic substance or catalyst after the reaction process or completion of the reaction, polymerizing it, and heating. An amorphous ceramic transparent film can be formed. A film formed using this metal alkoxide is useful as an organic film because of its high gas barrier property.

  In addition to the above alkoxysilane compounds, organic film forming materials include hexamethyldisiloxane, octatetramethylsilane, cyclopentasiloxane, decamethylcyclopentasiloxane, 2,2,5,5-tetramethyl-2 , 5-disila-1-oxacyclopentane, (cyclohexenyloxy) trimethylsilane, cyclopentadienyltrimethylsilane, cyclopentamethylenedimethylsilane, (cyclopentenyloxy) trimethylsilane, cyclotetramethyldimethylsilane, cyclotrimethylene An organosilicon compound such as dimethylsilane can be used.

  In the present invention, the organic film forming material preferably has a cardo polymer. As a result, the adhesion between the organic film and the first inorganic film and the second inorganic film can be improved, and the pinholes existing in the first inorganic film and the second inorganic film are filled more effectively. Because it can. In addition, since the organic film with good flatness is formed by having the cardo polymer, the second inorganic film is formed more densely on the organic film, so that the gas barrier property is increased. Because it can.

  Examples of such cardo polymers include (i) an addition product of an epoxy acrylate resin having a fluorene skeleton and a polybasic acid anhydride, (ii) a polyfunctional acrylate monomer, (iii) a polymerization initiator, and (iv) The thing which has as an essential component the epoxy resin which has 2 or more of epoxy groups in 1 molecule is mentioned.

  The cardo polymer used in the present invention preferably contains a resin having a fluorene skeleton derived from a bisphenol compound represented by the following general formula (1).

(R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different.)

  Specific examples of the bisphenol compound represented by the general formula (1) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). ) Fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) ) Fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3) , 5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc., and these can be used alone or in combination of two or more Can also be used together.

  In the present invention, the cardo polymer comprises an epoxy (meth) acrylate resin obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an unsaturated monocarboxylic acid, a polybasic acid anhydride, An epoxy (meth) acrylate acid adduct derived from is preferable.

  Specific examples of the epoxy resin used for forming such an epoxy (meth) acrylate acid adduct include bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, and 2,2-bis (4 -Hydroxyphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, bis (4-hydroxyphenyl) dimethylsilane, 4 , 4'-biphenol, tetramethyl-4,4'-biphenol and other bisphenols, phenol novolac, cresol novolac, naphthol or naphthalenediol and polyfunctional phenols such as condensation compounds of 1,4-bisxylenol, Some or all of these aromatic ring hydrogens are halogen atoms and alkyls having 1 to 4 carbon atoms. Include those having two or more epoxy groups polyfunctional phenols substituted in one molecule obtained by reacting with epichlorohydrin. This epoxy resin can be converted into an epoxy (meth) acrylate resin by reacting an acrylic acid equivalent to the epoxy resin with acrylic acid such as acrylic acid or methacrylic acid by a known method. By making it react with a polybasic acid anhydride, it can be set as the addition product of an epoxy (meth) acrylate resin and a polybasic acid anhydride.

  Specific examples of polybasic acid anhydrides used in the formation of such addition products include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acids, cycloaliphatic anhydrides such as methylcyclohexene dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bistrimellitic anhydride, glycerol tris And aromatic acid anhydrides such as trimellitate anhydride and biphenyltetracarboxylic dianhydride, and halogen acid anhydrides such as het anhydride and tetrabromophthalic anhydride. Further, the epoxy resin, acrylate, and acid anhydride may be one kind or a mixture of two or more kinds.

  Among the epoxy (meth) acrylate acid adducts thus obtained, in the present invention, as seen in JP-A-60-152091, JP-A-6-1938, JP-A-846311. In addition, it is preferable that a resin having a weight average molecular weight of 1000 or more having a carboxyl group and a photopolymerizable unsaturated group in the same molecule is contained in the organic film. Specific examples include acid addition products of Nippon Steel Chemical Co., Ltd., V259M and V301M, which are epoxy acrylate acid adducts having a fluorene skeleton, and Nippon Kayaku Co., Ltd. cresol novolac type epoxy acrylate acid adducts.

  As the epoxy acrylate resin having the fluorene skeleton, one obtained by reacting an epoxy resin obtained from 9,9-bis (4-hydroxyphenyl) fluorene with acrylic acid is preferably used.

  Further, as the above-mentioned polyfunctional acrylate monomer used in the present invention, specifically, addition polymerization having a boiling point of 100 ° C. or higher at normal pressure and having at least two ethylenically unsaturated groups in one molecule. What is a compound is mentioned. Examples of such materials include those obtained by combining a polyhydric alcohol and an α, β-unsaturated carboxylic acid, such as diethylene glycol (meth) acrylate (meaning diacrylate or dimethacrylate, hereinafter the same), tri Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-propanediol (Meth) acrylate, 1,3-butanediol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Polyfunctional acrylates such as thiophene, corresponding polyfunctional methacrylates, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, 2,2-bis (4-Methacryloxypolyethoxyphenyl) propane mixture (trade name: BEP-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and glycyl group-containing compounds such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids For example, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and an acrylic acid adduct of diglycidyl ether having a fluorene ring (Nippon Steel Chemical ( Product name: ASF400), etc., and unsaturated amides such as methylenebisacrylamide, 1,6-hexamethylene Scan acrylamide or vinyl esters such as divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate, and the like.

  Here, the composition of the organic film is not particularly limited as long as it has a cardo polymer as described above. Therefore, when the organic film has a thermosetting resin, a thermopolymerization initiator is used as the polymerization initiator, and when the organic film has a photocurable resin, a photopolymerization initiator is used as the polymerization initiator.

  As such a photopolymerization initiator, known ones can be used alone or in combination of several kinds. For example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON (commercially available product Irgacure 907 manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (commercial product Irgacure 369 manufactured by Ciba Specialty Chemicals), bis (2, 4,6-trimethylbenzoyl) phenylphosphine oxide (trade name CGI819 manufactured by Ciba Specialty Chemicals), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF Lucirin TPO), 2,4-trichloromethyl- (piprolonyl)- 6-triazine (commercially available product, trade name Triazine PP, manufactured by Nippon Sebel Hegner) can be used.

  In addition, as a thermal polymerization initiator, a radical is generated when heated, and a thermosetting resin having a cardo polymer and a unsaturated group of a polyfunctional acrylate monomer can be polymerized to form a cured film. However, the 10-hour half-life temperature is preferably 80 ° C. or more and the curing temperature or less, more preferably 100 ° C. or more and the curing temperature.

  Furthermore, as the epoxy resin having two or more epoxy groups in one molecule, an epoxy compound having a hydrolyzable chlorine content of less than 1000 ppm is preferable. For example, YX4000 tetramethyldiphenyl type epoxy resin manufactured by Yuka Shell Co., Ltd. , EOCN series (EOCN1020, 4400, 102S, 103S, 104S, etc.) manufactured by Nippon Kayaku Co., Ltd. The polyfunctional epoxy compound which introduce | transduced the glycidyl group into the secondary hydroxyl group in an epoxy compound etc. are mentioned. In such an epoxy resin, the epoxy group reacts with the carboxyl group in the resin component containing the cardo polymer by heating or the like, and has a crosslinked structure in addition to the unsaturated group of the resin containing the cardo polymer and the polyfunctional acrylate. To form.

  Moreover, in this invention, additives, such as antioxidant, a ultraviolet absorber, a plasticizer, can be added to the material of the organic film mentioned above as needed. In addition, an appropriate resin or additive may be used to improve film formability and prevent pinhole formation. Furthermore, when forming an organic film, it can be prepared by dissolving or dispersing in a solvent such as diethylene glycol dimethyl ether, cyclohexanone, ethanol, chloroform, tetrahydrofuran, or dioxane.

  The method of forming the organic film is not particularly limited, and is a dry coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, a wet coating method using a roller coater, a land coater, or a vapor deposition method. A coating method can be used.

  In the present invention, the thickness of the organic film is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.5 to 10 μm. Under the present circumstances, when the said organic film is formed by the wet coating method, it is preferable to exist in the range of 0.5-10 micrometers, especially in the range of 1 micrometer-5 micrometers. Moreover, when formed by the dry coating method, it is preferable that it exists in the range of 0.05 micrometer-5 micrometers, especially in the range of 0.05 micrometer-1 micrometer. When the film thickness of the organic film formed by the wet coating method or the dry coating method is within the above-described range, the adhesion between the first inorganic film and the second inorganic film can be improved. Because. Moreover, when the film thickness of the organic film is smaller than the above range, the pinholes of the first inorganic film or the second inorganic film may not be sufficiently filled, and the gas barrier property may be lowered. . On the other hand, when the thickness of the organic film is larger than the above range, the thickness of the antireflection gas barrier substrate is increased, and the total light transmittance may be lowered.

  The refractive index of the resin that is the material for forming the organic film is usually 1.3 to 1.6. In the present invention, the refractive index of the organic film is the above-described first inorganic film and the first inorganic film. 2 Since the value is preferably close to the refractive index of the inorganic film, it is preferably in the range of 1.4 to 1.6. This is because if the difference in refractive index between the first inorganic film and the second inorganic film and the organic film is large, the reflection of light increases at the interface between the respective films, and the total light transmittance may decrease. .

  The flatness of the organic film is preferably such that the surface average roughness (Ra) is 5 nm or less, particularly 1 nm or less, and the maximum height difference (P-V) is 50 nm or less, particularly 10 nm or less. Is preferred. When the surface roughness and the maximum height difference of the organic film are within the above-described range, when the second inorganic film described above is formed on the organic film, it can be formed densely and flatly, This is because the gas barrier property can be increased. The gas barrier property is related to two mechanisms of adsorption (dissolution) and diffusion, and when the surface of the organic film is flattened, adsorption (dissolution) and diffusion on the surface of the organic film are suppressed. Furthermore, when using the antireflective gas barrier substrate of the present invention as an organic EL element, for example, a transparent conductive layer may be formed on the second inorganic film, but there are irregularities in the second inorganic film. This uneven shape is also reflected in the transparent conductive layer formed on the second inorganic film, and defects due to electrostatic breakdown or the like are likely to occur in the thin organic EL element. Such a defective portion becomes a defective portion (dark area), which causes a reduction in display quality. Therefore, when the surface roughness and the maximum height difference of the organic film are within the above-described range, it is possible to suppress the occurrence of the dark area as described above, and the organic film is formed using the antireflection gas barrier film of the present invention. This is because when an EL element is used, a good image display can be obtained.

  Here, the surface roughness and the maximum height difference are values measured using an atomic microscope (Nanopics: trade name, manufactured by Seiko Instruments Inc.) under the conditions of a scanning range of 100 μm and a scanning speed of 90 sec / frame.

  In the present invention, depending on the method for forming the first inorganic film and the material for forming the organic film, the effects of adhesion and gas barrier properties between the first inorganic film and the organic film are different. For example, when the first inorganic film is formed by the ion plating method, when an organic film is formed on the first inorganic film, if a material having a hydroxyl group is used for the organic film, the hydroxyl group causes a hydrolysis reaction. Thus, an organic film having a glass-like high degree of oxidation is considered to improve the gas barrier property. Further, when the first inorganic film is formed by a sputtering method, by providing an organic film on the first inorganic film, fine pinholes and the like of the first inorganic film are filled, so that the gas barrier property is improved. Furthermore, when the first inorganic film is formed by plasma chemical vapor deposition, it is considered that the affinity between the two films is improved by providing an organic film on the first inorganic film.

5). Other (Laminated structure)
In the present invention, the deposited film and the organic film may be formed on the organic film described above, and the uppermost layer may be the second inorganic film. For example, as shown in FIG. 2, a first inorganic film 2 is formed on a substrate 1, an organic film 3 is formed on the first inorganic film 2, a vapor deposition film 5 is formed on the organic film 3, The organic film 3 may be formed on the vapor deposition film 5, the second inorganic film 4 may be formed on the organic film 3, and the uppermost layer may be the second inorganic film 4.

  This is because the gas barrier property is improved by further laminating the vapor deposition film and the organic film between the organic film and the second inorganic film as described above. Further, in the present invention, in the configuration of the film formed on the substrate, the antireflection is achieved by adjusting the film thickness and refractive index of the first inorganic film as the lowermost layer and the second inorganic film as the uppermost layer. The reflection of light on the gas barrier substrate can be suppressed, and the decrease in the total light transmittance can be suppressed. Therefore, even when the vapor deposition film and the organic film are laminated as described above, when the antireflection gas barrier substrate of the present invention is used for an organic EL element, for example, there is no defect such as a dark spot because the gas barrier property is high. In addition, since the reflection of light is suppressed, it is possible to obtain a good image display with high luminance.

  Further, the order of the vapor deposition film and the organic film needs to be alternately laminated. In the present invention, the first inorganic film, the second inorganic film, and the vapor deposition film are formed by forming an organic film between the first inorganic film or the second inorganic film and the vapor deposition film or between the two vapor deposition films. This is because the pinhole can be filled and oxygen and water vapor can be prevented from entering.

  Furthermore, the number of the deposited films and organic films is preferably in the range of 2 to 6 layers. When the deposited film and the organic film are laminated beyond the above range, the thickness of the antireflection gas barrier substrate of the present invention increases or the interface of the film increases, so that light reflection is likely to occur. This is because the total light transmittance may be lowered.

  As a material for forming such a vapor deposition film, the same material as the first inorganic film and the second inorganic film described above can be used. Further, the film thickness of the vapor deposition film is not particularly limited, unlike the first inorganic film and the second inorganic film, but is usually in the range of 10 nm to 500 nm. When the film thickness of the vapor deposition film is thinner than the above range, it is insufficient to improve the gas barrier property against water vapor, oxygen, etc., and when the film thickness of the vapor deposition film is thicker than the above range, This is because cracks or the like may occur when the antireflective gas barrier substrate of the present invention is produced, and this causes deterioration of gas barrier properties against water vapor, oxygen gas, and the like.

  Note that the organic film used in the case of being stacked is the same as the above-described organic film, and thus description thereof is omitted here.

(Stress relaxation layer)
In the antireflective gas barrier substrate of the present invention, a stress relaxation layer for relaxing stress applied to the substrate is formed on the surface of the substrate opposite to the surface on which the first inorganic film is formed. Is preferred. For example, as shown in FIG. 3, the first inorganic film 2, the organic film 3, and the second inorganic film 4 are sequentially formed on the substrate 1, and the surface of the substrate 1 on which the first inorganic film 2 is formed. The stress relaxation layer 6 is formed on the opposite surface. As a result, the stress generated when the first inorganic film, the organic film, and the second inorganic film are formed can be reduced, and warpage of the antireflection gas barrier substrate can be prevented. It is.

  Such a stress relieving layer is not particularly limited as long as it can relieve stress, but in the present invention, it is preferably formed by a vapor deposition method. As a material used for the vapor deposition method, for example, those described in the first inorganic film and the second inorganic film described above can be used. Thereby, since the gas barrier property can be imparted to the surface opposite to the surface on which the first inorganic film or the like of the antireflective gas barrier substrate is formed, the antireflective gas barrier substrate having a higher gas barrier property is obtained. Because you can. At this time, the stress relaxation layer is not limited to one layer, and may be, for example, a laminate of the above-described deposited film and organic film.

  The thickness of the stress relaxation layer is preferably about the same as the total thickness of the first inorganic film, the second inorganic film, and the deposited film formed on the substrate. The total thickness of the first inorganic film, the second inorganic film, and the deposited film is preferably within a range of ± 200 nm. Thereby, the stress generated when the first inorganic film, the organic film, the second inorganic film and the like are effectively formed can be reduced, and the antireflection gas barrier substrate can be prevented from warping. Because it can. In addition, since the stress by an organic film is small compared with the stress by a 1st inorganic film and a 2nd inorganic film as a stress concerning a base material, when setting the film thickness of a stress relaxation layer, the film thickness of an organic film Will not be taken into account.

(Anti-reflective gas barrier substrate)
In the present invention, the surface average roughness of the antireflection gas barrier substrate is preferably 5 nm or less, particularly 1 nm or less, and the maximum height difference is preferably 50 nm or less, particularly 10 nm or less. When the antireflection gas barrier substrate of the present invention is used to form, for example, an organic EL element, a transparent conductive layer may be formed on the antireflection gas barrier substrate, but when there are irregularities on the antireflection gas barrier substrate, This uneven shape is also reflected in the transparent conductive layer formed on the antireflection gas barrier substrate, and defects due to electrostatic breakdown or the like are likely to occur in a thin organic EL element. Although such a defective part becomes a dark area, when the average surface roughness and the maximum height difference of the antireflection gas barrier substrate are within the above range, the occurrence of this dark area can be suppressed, and When a display element is formed using an antireflection gas barrier substrate, a good image display can be obtained. As a result, the antireflection gas barrier substrate of the present invention can be used for various applications such as a liquid crystal display element and a display substrate for an organic EL element.

  Here, the surface roughness and the maximum height difference are values measured using an atomic microscope (Nanopics: trade name, manufactured by Seiko Instruments Inc.) under the conditions of a scanning range of 100 μm and a scanning speed of 90 sec / frame.

B. Next, the display substrate of the present invention will be described. The display substrate of the present invention uses the above-described antireflection gas barrier substrate.

  According to the present invention, since the above-described antireflection gas barrier substrate is used, by having an antireflection function, it is possible to obtain a display substrate having a high total light transmittance and a high gas barrier property. It can be used.

  The display substrate of the present invention preferably has a transparent conductive layer on the antireflection gas barrier substrate. As a formation position of the transparent conductive layer, it may be formed on the second inorganic film of the antireflection gas barrier substrate, or may be formed on a substrate.

  In the present invention, it is particularly preferable that the transparent conductive layer is formed on the substrate. Since a transparent conductive layer can be formed as a stress relaxation layer that relieves stress generated when the first inorganic film, the organic film, and the second inorganic film of the antireflection gas barrier substrate are formed, This is because the layer structure can be simplified and a display substrate can be efficiently manufactured.

  The transparent conductive layer used in the present invention may be an anode or a cathode as long as it is a transparent conductive layer with respect to visible light, and is appropriately selected according to the use of the display substrate of the present invention. Is.

  Specifically, as such a transparent conductive layer, indium tin oxide (ITO), indium zinc oxide (IZO), or the like is preferably used. These transparent conductive layers can be formed by a PVD method such as a vacuum deposition method, a sputtering method, or an ion plating method.

  The film thickness of the transparent conductive layer used in the present invention is preferably in the range of about 50 nm to 500 nm. When the thickness of the transparent conductive layer is smaller than the above, a decrease in conductivity is observed, and when the thickness of the transparent electrode layer is thicker than the above, as the post-processing steps proceed, the conductive film cracks, etc. This is because it is not preferable because of deterioration of conductivity. In addition, when the transparent conductive layer is formed as a stress relaxation layer, it is preferable that it becomes the film thickness described in the column of the stress relaxation layer mentioned above.

  As the display element in which the display substrate of the present invention is used, a non-luminous display such as a liquid crystal display element that performs display with gradation by shuttering the brightness of a backlight, a plasma display (PDP), Examples thereof include self-luminous displays such as a field emission display (FED) and an electroluminescence display (EL) that perform display by illuminating a phosphor with some energy.

C. Next, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention has the display substrate.

  According to the present invention, since the display substrate is not affected by oxygen, water vapor, or the like even over time, the display quality does not deteriorate and the total light transmittance is obtained because of having an antireflection function. And a high-quality liquid crystal display element capable of obtaining a high-luminance image display.

  FIG. 4 shows an example of the liquid crystal surface element of the present invention. As shown in FIG. 4, the liquid crystal display element of the present invention has two display substrates 10. The display substrate 10 includes a base material 1, a first inorganic film 2 formed on the base material 1, an organic film 3 formed on the first inorganic film 2, and an organic film 3 on the organic film 3. It has the formed 2nd inorganic film | membrane 4 and the transparent conductive layer 11 formed in the surface on the opposite side to the surface in which the 1st inorganic film | membrane 2 of the said base material 1 is formed. The two display substrates 10 are arranged so that the transparent conductive layers 11 face each other. On the transparent conductive layer 11, alignment films 12 having a role for regularly arranging liquid crystal molecules are respectively provided. Is formed. Further, the display substrate 10 is bonded through a sealing material 15, and a liquid crystal material 14 is sealed between the two display substrates 10 inside the sealing material 15. Further, a plurality of spacers 16 are provided between the alignment films 12 of the two display substrates 10. In addition, a deflection plate 13 is provided on each of the second inorganic films 4 of the two display substrates 10.

  If the liquid crystal display element of this invention has the said board | substrate for a display, a layer structure will not be specifically limited, According to the use etc. of a liquid crystal display element, it selects suitably.

  Examples of the material constituting the alignment film used in the present invention include inorganic substances such as silicon oxide, aluminum oxide, zirconia, magnesium fluoride, cerium oxide, cerium fluoride, silicon nitride, silicon carbide, and boron nitride, and polyimide. Organic materials such as acrylic resins are used.

  Moreover, as a sealing material used for this invention, an organic type sealing material is normally used.

  Furthermore, the spacer used in the present invention may be an inorganic spacer or an organic spacer. Further, examples of the shape of the spacer include a rod shape, a spherical shape, and a column shape.

  In FIG. 4, the deflecting plates are formed on the second inorganic films of the two display substrates. However, in the present invention, either one of the two inorganic films on the two display substrates is used. It may be formed only on.

D. Organic EL Element Next, the organic EL element of the present invention will be described. The organic EL element of the present invention has the display substrate.

  According to the present invention, since the display substrate is included, it is not affected by oxygen, water vapor, or the like over time, and there is no defect such as a dark spot, and since it has an antireflection function, it transmits all light. It is possible to obtain a high-quality organic EL element having a high rate and capable of obtaining a high-luminance image display.

  As long as the organic EL element of the present invention has an organic EL layer formed on the transparent conductive layer of the display substrate and a counter electrode formed on the organic EL layer, the layer structure is particularly It is not limited, It selects suitably according to the use etc. of an organic EL element.

  Here, the organic EL layer referred to in the present invention can be one normally used for an organic EL element, and is formed from one or a plurality of organic layers including at least a light emitting layer. That is, the organic EL layer is a layer including at least a light emitting layer, and the layer configuration is a layer having one or more organic layers. Usually, when an organic EL layer is formed by a wet method by coating, it is often difficult to stack a large number of layers in relation to a solvent, so that it is often formed of one or two organic layers. However, it is possible to further increase the number of layers by devising organic materials or combining vacuum deposition methods.

  As the organic layer formed in the organic EL layer other than the light emitting layer, a layer usually used for the organic EL layer can be used, and examples thereof include a charge injection layer such as a hole injection layer and an electron injection layer. it can. Furthermore, examples of the other organic layers include a charge transport layer such as a hole transport layer that transports holes to the light-emitting layer and an electron transport layer that transports electrons to the light-emitting layer. In many cases, it is formed integrally with the charge injection layer by imparting a charge transporting function. In addition, examples of the organic layer formed in the EL layer include a layer for preventing the penetration of holes or electrons, such as a carrier block layer, and improving the recombination efficiency.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

[Example 1]
(Formation of first inorganic film)
The transparent substrate was placed in the chamber of the magnetron sputtering apparatus. Silicon nitride was used as a target, and film formation was performed under the following film formation conditions until the silicon oxynitride film thickness reached 100 nm.
Deposition pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 20 sccm
Nitrogen gas flow rate: 9sccm
Frequency: 13.56MHz
Electric power: 1.2kW

(Formation of organic film)
On the first inorganic film, a resin having a cardo polymer having a fluorene skeleton was applied by spin coating, and heated at 160 ° C. for 1 hour to form an organic film. The film thickness of the organic film was 1 μm on the first inorganic film. At this time, the first inorganic film was not deformed, and the organic film had a surface roughness Ra of 0.8 nm and a maximum height difference PV of 8 nm.

(Formation of second inorganic film)
A second inorganic film was formed on the organic film in the same manner as the first inorganic film. Thereby, an antireflection gas barrier substrate was obtained.

(Formation of transparent conductive layer)
An ITO film was formed by sputtering on the surface of the antireflection gas barrier substrate opposite to the surface on which the first inorganic film or the like was formed. Thus, a display substrate was obtained.

(Production of liquid crystal display element)
An alignment film is formed on the transparent conductive layer of the display substrate, the two display substrates are opposed to each other, bonded together with a sealing material, and a liquid crystal material is sealed between them, thereby displaying a liquid crystal display An element was produced.

[Examples 2 to 5]
A liquid crystal display element was produced in the same manner as in Example 1 except that the film thickness of the first inorganic film and the film thickness of the second inorganic film were set as shown in Table 1.

[Example 6]
(Formation of first inorganic film)
The transparent substrate was placed in the chamber of the magnetron sputtering apparatus. Silicon was used as a target, and deposition was performed under the following deposition conditions until the thickness of the silicon oxynitride film reached 100 nm.
Deposition pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
Nitrogen gas flow rate: 20sccm
Frequency: 13.56MHz
Electric power: 1.2kW

(Formation of organic film)
In the same manner as in Example 1, an organic film was formed on the first inorganic film.

(Formation of second inorganic film)
A second inorganic film was formed on the organic film in the same manner as the first inorganic film. Thereby, an antireflection gas barrier substrate was obtained.

(Formation of transparent conductive layer)
In the same manner as in Example 1, an ITO film was formed on the surface of the antireflection gas barrier substrate opposite to the surface on which the first inorganic film or the like was formed, to obtain a display substrate.

(Production of liquid crystal display element)
A liquid crystal display element was produced in the same manner as in Example 1.

[Example 7]
(Formation of first inorganic film)
The transparent substrate was placed in the chamber of the ion plating apparatus. Silicon oxide was used as the sublimation material, and film formation was performed under the following film formation conditions until the silicon oxynitride film thickness reached 100 nm.
Deposition pressure: 1.5 × 10 ⁻¹ Pa
Argon gas flow rate: 12sccm
Nitrogen gas flow rate: 20sccm
Deposition current value: 100A

(Formation of organic film)
In the same manner as in Example 1, an organic film was formed on the first inorganic film.

(Formation of second inorganic film)
A second inorganic film was formed on the organic film in the same manner as the first inorganic film so as to have a film thickness of 50 nm. Thereby, an antireflection gas barrier substrate was obtained.

(Formation of transparent conductive layer)
In the same manner as in Example 1, an ITO film was formed on the surface of the antireflection gas barrier substrate opposite to the surface on which the first inorganic film or the like was formed, to obtain a display substrate.

(Production of liquid crystal display element)
A liquid crystal display element was produced in the same manner as in Example 1.

[Example 8]
A liquid crystal display element was produced in the same manner as in Example 7 except that the thickness of the first inorganic film was 150 nm.

[Comparative Example 1]
A liquid crystal display element was produced in the same manner as in Example 1 except that the film thickness of the first inorganic film was 70 nm and the film thickness of the second inorganic film was 30 nm.

[Comparative Example 2]
A liquid crystal display element was produced in the same manner as in Example 1 except that the thickness of the first inorganic film was 50 nm and the thickness of the second inorganic film was 50 nm.

[Comparative Example 3]
A liquid crystal display element was produced in the same manner as in Example 1 except that the film thickness of the first inorganic film was 800 nm and the film thickness of the second inorganic film was 50 nm.

[Evaluation]
Table 1 shows the evaluation results of luminous reflectance, total light transmittance, oxygen transmittance and water vapor transmittance in the visible light region of the antireflection gas barrier substrate in the liquid crystal display elements of Examples 1 to 8 and Comparative Examples 1 to 3. Show.

  As is apparent from Table 1, in the liquid crystal display elements of Examples 1 to 8, reflection is suppressed, the total light transmittance is high, and the gas barrier property is high, so that it is possible to obtain a high-brightness and good image display. It was.

It is a schematic sectional drawing which shows an example of the antireflection gas barrier property board | substrate of this invention. It is a schematic sectional drawing which shows the other example of the antireflection gas barrier property board | substrate of this invention. It is a schematic sectional drawing which shows the other example of the antireflection gas barrier property board | substrate of this invention. It is a schematic sectional drawing which shows an example of the liquid crystal display element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... 1st inorganic film 3 ... Organic film 4 ... 2nd inorganic film

Claims (12)

A base material; a first inorganic film formed on the base material; an organic film formed on the first inorganic film; and a second inorganic film formed on the organic film. The luminous reflectance in the visible light region is 20% or less, the total light transmittance is 80% or more, the oxygen transmittance is 0.5 cc / m ² · day or less, and the water vapor transmission rate is 0.5 g / m ² · day or less. An antireflective gas barrier substrate characterized by the above. The optical film thickness (film thickness × refractive index) of the first inorganic film is in the range of 140 nm to 1000 nm, and the optical film thickness (film thickness × refractive index) of the second inorganic film is in the range of 10 nm to 1000 nm. The antireflection gas barrier substrate according to claim 1, wherein The antireflection gas barrier property according to claim 2, wherein the thickness of the first inorganic film is in a range of 80 nm to 500 nm, and the thickness of the second inorganic film is in a range of 10 nm to 500 nm. substrate. The antireflective gas barrier substrate according to claim 2, wherein the refractive index of the first inorganic film and the second inorganic film is in a range of 1.2 to 2.0. The antireflective gas barrier substrate according to any one of claims 1 to 4, wherein the first inorganic film and the second inorganic film are a silicon oxide film or a silicon oxynitride film. . The antireflection gas barrier substrate according to any one of claims 1 to 5, wherein the organic film contains a cardo polymer. The vapor deposition film and the organic film are laminated on the organic film in the order of 2 to 6 layers in this order, and the uppermost layer is the second inorganic film. The antireflection gas barrier substrate according to any one of claims 6 to 6. The stress relaxation layer which relieve | moderates the stress concerning the said base material is formed in the surface on the opposite side to the surface in which the said 1st inorganic film | membrane was formed in the said base material. The antireflection gas barrier substrate according to any one of claims 7 to 7. A display substrate comprising the antireflection gas barrier substrate according to any one of claims 1 to 8. The display substrate according to claim 9, wherein the stress relaxation layer in the antireflection gas barrier substrate according to claim 8 is a transparent conductive layer. A liquid crystal display element comprising the display substrate according to claim 9. An organic EL device comprising the display substrate according to claim 9.

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