JP2009038019A - Gas barrier sheet, gas barrier sheet manufacturing method, sealing body, and organic EL display - Google Patents

Abstract

A gas barrier sheet having a gas barrier property and a heat dissipation property, a method for producing the gas barrier sheet, a sealing body using the gas barrier sheet, and An organic EL display using a sealing body is provided.
An exothermic object to be sealed 5 provided on a substrate 7 and a gas barrier sheet 1A provided on the object 5 to be sealed, at least the gas barrier sheet 1A and the object to be sealed The sealing body 10A to which the surface of the substrate 7 around the object 5 is bonded, wherein the gas barrier sheet 1A has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 The above problem is solved by setting the power to 30 W / mK or more.
[Selection] Figure 3

Description

  The present invention relates to a gas barrier sheet, a method for producing the gas barrier sheet, a sealing body using the gas barrier sheet, and an organic EL display using the sealing body.

  Development of gas barrier sheets used for displays and the like has been conventionally performed.

  Patent Document 1 relates to a technique for protecting a barrier layer of a front-side sealing film by a thickness ratio between a front-side sealing film and a back-side sealing film covering a display element. Specifically, the sealing film of a transparent display element having excellent barrier properties with less cracking due to a difference in bending of the film during heat sealing depending on the ratio of the thickness of the stretched film on the front side and the stretched film on the back side Is provided.

  Patent Document 2 provides a water vapor barrier film suitable for producing an organic EL device that is light and lightweight and shielded from moisture in the outside world, and provides an organic EL device using the water vapor barrier film. It is said. In the same document, in order to solve the above problems, in the water vapor barrier film having the water vapor barrier laminate on the base film, the water vapor barrier laminate is made of silicon, aluminum, zinc, tin, and lead. And a barrier layer mainly composed of at least one compound selected from the group consisting of oxides and oxynitrides. When the water vapor barrier laminate is composed of only one barrier layer, the barrier layer contains at least one alkali metal oxide. On the other hand, when the water vapor barrier laminate is composed of two or more layers, at least one kind of alkali metal oxide is contained in at least one layer selected from the barrier layer and a layer adjacent to the barrier layer. I am doing so.

Patent document 3 makes it a subject to provide the sealing means which can implement | achieve a sufficiently advanced barrier, without impairing flexibility with respect to a film organic EL element. In this document, in order to solve the above problems, a film substrate made of a plastic film having a barrier layer, a transparent electrode (anode), a hole transport layer, a light emitting layer, a metal electrode ( A film organic EL element comprising a light emitting functional layer composed of a cathode) and a sealing means for sealing the light emitting functional layer is used. The sealing means includes a sealing film made of a barrier inorganic thin film formed so as to cover the entire light emitting functional layer, and a barrier layer bonded to the sealing film via an adhesive. The sealing film is made of a plastic film. Further, a silicon nitride film (SiNx) or a silicon oxynitride film (SiOxNy) is used as the sealing film and the barrier layer.
JP 2007-66686 A (Claim 1, paragraph 0006, paragraph 0007) JP 2007-90702 A (Claim 1, paragraph 0005) Japanese Patent Laying-Open No. 2005-339863 (claims 1 to 3, paragraph 0007)

  As described above, Patent Documents 1 to 3 introduce technologies that focus on improving the gas barrier properties of organic EL display elements. However, according to the study of the present inventor, it has been found that there is still an insufficient point as a gas barrier sheet used in a display device such as an organic EL display only by having a predetermined gas barrier property. That is, according to the study of the present inventors, it has been found that a gas barrier sheet used in a display device such as an organic EL display needs to have not only high gas barrier properties but also high heat dissipation properties.

  The organic EL display element is sealed with a gas barrier sheet and has a sealed structure in order to suppress generation of dark spots and the like due to moisture intrusion. On the other hand, light emission in the element is performed by recombination of holes and electrons. However, since the light emission efficiency does not become 100%, a part of energy generated by the recombination becomes heat. And since heat | fever generate | occur | produced as a loss at the time of light emission will inevitably stay in an organic EL display element by the amount which employ | adopts said sealing structure.

  However, organic EL display elements composed of organic substances are generally vulnerable to heat. For this reason, if a long time or a large amount of heat stays inside the organic EL display element, malfunction or destruction of the element is caused. For this reason, according to examination of this inventor, in an organic EL display element, it turned out that it becomes an important subject to provide a heat dissipation function to the gas barrier sheet | seat which seals the element. And the subject which needs provision of such a heat dissipation function is not restricted only to an organic EL display element, The display element which has exothermic property, such as a liquid crystal display, and the exothermic element, such as an organic EL lighting element, are gas-barrier sheets It also occurs in common when sealing and sealing.

  The present invention has been made to solve the above-mentioned problems, and a first object thereof is a gas barrier sheet having both gas barrier properties and heat dissipation properties, which is used in combination with an exothermic object to be sealed. Is to provide.

  The present invention has been made to solve the above problems, and a second object of the present invention is to provide a method for producing the gas barrier sheet.

  The present invention has been made to solve the above problems, and a third object of the present invention is to provide a sealing body using the gas barrier sheet.

  The present invention has been made to solve the above-mentioned problems, and a fourth object thereof is to provide an organic EL display using the above-described sealing body.

  The present inventor uses diamond-like carbon (DLC) as a material for the heat-dissipating gas barrier film, and further adjusts the thermal conductivity of the heat-dissipating gas barrier film by controlling the composition of the diamond-like carbon, thereby providing high gas barrier properties and high It has been found that a gas barrier sheet capable of achieving both heat dissipation can be obtained. Then, by applying such a gas barrier sheet to a heat-generating encapsulated material represented by a display element such as an organic EL display element or an illumination element such as an organic EL illumination element, a high-performance encapsulant is obtained. I found out that

  The gas barrier sheet of the present invention for solving the above problems is a gas barrier sheet for sealing an exothermic object to be sealed, and the gas barrier sheet is a heat dissipating gas barrier film made of diamond-like carbon. The thermal conductivity of the heat dissipating gas barrier film is 30 W / mK or more.

  According to this invention, the gas barrier sheet has a heat dissipating gas barrier film made of diamond-like carbon, and the heat dissipating gas barrier film has a thermal conductivity of 30 W / mK or more. As a result, it is possible to provide a gas barrier sheet having both a gas barrier property and a heat dissipation property, which can be combined with a heat generating material to be sealed.

  In a preferred embodiment of the gas barrier sheet of the present invention, the atomic ratio of carbon (C) and silicon (Si) in the heat dissipating gas barrier film is C: Si = 1000: 0 to 1000: 40.

  According to this invention, since the atomic ratio of carbon (C) and silicon (Si) in the heat dissipation gas barrier film is C: Si = 1000: 0 to 1000: 40, the heat conduction of the heat dissipation gas barrier film It becomes easy to make the rate 30 W / mK or higher, and as a result, it is possible to provide a gas barrier sheet having both gas barrier properties and heat dissipation properties, which can be combined with exothermic objects to be sealed.

  In a preferred embodiment of the gas barrier sheet of the present invention, the gas barrier sheet further has a second gas barrier film and / or a third gas barrier film, and the second gas barrier film and the third gas barrier film are: Each contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride.

  According to this invention, the gas barrier sheet further includes the second gas barrier film and / or the third gas barrier film, and the second gas barrier film and the third gas barrier film are respectively silicon nitride, silicon oxide, and acid. Since it contains at least one selected from silicon nitride, the heat dissipating gas barrier film can be combined with the second gas barrier film and the third gas barrier film, and the gas barrier property is further improved while maintaining the heat dissipating property. A high gas barrier sheet can be provided.

  In a preferred aspect of the gas barrier sheet of the present invention, the second gas barrier film is provided in contact with the heat dissipating gas barrier film.

  According to this invention, since the second gas barrier film is provided in contact with the heat-dissipating gas barrier film, the heat-dissipating gas barrier film and the second gas barrier film are used in a stacked manner, and the gas barrier is maintained while maintaining heat dissipation. A gas barrier sheet having higher properties can be provided.

  In a preferred embodiment of the gas barrier sheet of the present invention, the exothermic object to be sealed is any one of an organic EL display element, a liquid crystal display element, and an organic EL lighting element.

  According to this invention, since the exothermic object to be encapsulated is any one of an organic EL display element, a liquid crystal display element, and an organic EL lighting element, an encapsulant having a large exothermic property is used. As a result, the significance of applying the gas barrier sheet of the present invention increases.

  In a preferred embodiment of the gas barrier sheet of the present invention, the heat dissipation gas barrier film has an extinction coefficient of 0.00001 or more and 0.1 or less.

  According to this invention, since the extinction coefficient of the heat dissipating gas barrier film is 0.00001 or more and 0.1 or less, it becomes easy to ensure the transparency of the heat dissipating gas barrier film, and as a result, the gas barrier property having high transparency is achieved. A sheet can be obtained.

  In a preferred embodiment of the gas barrier sheet of the present invention, an anchor coating agent film provided on a substrate, the second gas barrier film provided on the anchor coating agent film, and the second gas barrier And the heat-dissipating gas barrier film provided on the film in this order.

  According to this invention, the anchor coating agent film provided on the base material, the second gas barrier film provided on the anchor coating agent film, and the second gas barrier film are provided. Since the heat-dissipating gas barrier film is provided in this order, the adhesiveness between the second gas barrier film and the substrate is ensured, and the flatness of the second gas barrier film and the heat-dissipating gas barrier film is easily ensured. As a result, a gas barrier sheet having a higher gas barrier property can be provided.

  In a preferred embodiment of the gas barrier sheet of the present invention, the third gas barrier film is provided on the surface of the base material on which the anchor coat agent film is not provided.

  According to this invention, the third gas barrier film is used together with the second gas barrier film because the third gas barrier film is provided on the surface of the base material on which the anchor coating agent film is not provided. As a result, a gas barrier sheet having a higher gas barrier property can be provided.

  In a preferred embodiment of the gas barrier sheet of the present invention, an antistatic film is further provided.

  According to the present invention, since the antistatic film is further provided, static electricity generated in the organic EL display element and the organic EL lighting element can be easily neutralized, or dust and dust can be prevented from attaching. As a result, a gas barrier sheet with higher functionality can be provided.

  The method for producing a gas barrier sheet of the present invention for solving the above problems is a method for producing a gas barrier sheet of the present invention, comprising a diamond-like carbon and having a heat conductivity of 30 W / mK or more. It has a heat-dissipating gas barrier film forming step for forming a film.

  According to the present invention, since the heat-dissipating gas barrier film forming step of forming a heat-dissipating gas barrier film made of diamond-like carbon and having a thermal conductivity of 30 W / mK or more is provided, the predetermined heat-dissipating gas barrier film is satisfactorily formed. As a result, a method for producing a gas barrier sheet with high industrial productivity can be provided.

  In a preferred aspect of the method for producing a gas barrier sheet according to the present invention, the heat dissipating gas barrier film forming step is performed by a plasma CVD method using a pressure gradient type holocathode as a plasma source.

  According to the present invention, the heat dissipating gas barrier film forming step is performed by the plasma CVD method using the pressure gradient type holocathode as a plasma source, so that high-density plasma can be generated. It becomes easy to ensure transparency.

  In order to solve the above problems, a sealed body of the present invention has a heat-generating sealed object provided on a substrate and a gas barrier sheet of the present invention provided on the sealed object. In addition, at least the gas barrier sheet and the substrate surface around the object to be sealed are adhered to each other.

  According to this invention, since the gas barrier sheet of the present invention is used, the heat dissipating gas barrier film comes to have both the gas barrier property and the heat dissipating property. The sealing body which can ensure heat dissipation can be provided.

  In a preferred embodiment of the sealing body of the present invention, the exothermic object to be sealed is an organic EL display element, and the cathode or anode of the organic EL display element and the heat dissipating gas barrier film face each other. Provided.

  According to the present invention, the exothermic object to be sealed is an organic EL display element, and the cathode or anode of the organic EL display element and the heat dissipating gas barrier film are provided to face each other. It is easy for heat generated from the heat to escape through the heat dissipating gas barrier film, and as a result, it is possible to provide a sealed body with higher heat dissipation efficiency.

  In the preferable aspect of the sealing body of this invention, the cathode or anode of the said organic EL display element, and the said heat-radiating gas barrier film are adhere | attached through the heat conductive adhesive agent.

  According to this invention, since the cathode or anode of the organic EL display element and the heat dissipating gas barrier film are bonded via the heat conductive adhesive, the heat generated from the organic EL display element is thermally conductive. It becomes easy to escape through the adhesive and the heat dissipating gas barrier film, and as a result, a sealed body with higher heat dissipating efficiency can be provided.

  The organic EL display of the present invention for solving the above-described problems has the sealing body of the present invention.

  According to this invention, since the organic EL display of the present invention has the sealing body of the present invention, an organic EL display element having a large exothermic property is used as an object to be sealed, and as a result, good gas barrier properties and heat dissipation are achieved. It is possible to provide an organic EL display capable of ensuring the performance.

  According to the gas barrier sheet of the present invention, it is possible to provide a gas barrier sheet having both a gas barrier property and a heat radiating property, which can be well combined with an exothermic object to be sealed.

  According to the method for producing a gas barrier sheet of the present invention, it is possible to provide a production method capable of producing the gas barrier sheet satisfactorily.

  According to the sealing body of the present invention, it is possible to provide a sealing body capable of ensuring good gas barrier properties and heat dissipation properties for an exothermic object to be sealed.

  According to the organic EL display of the present invention, it is possible to provide an organic EL display capable of ensuring a good gas barrier property and heat dissipation for an exothermic organic EL display element.

  Next, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(First aspect of gas barrier sheet)
FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier sheet of the present invention.

  The gas barrier sheet 1A has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 is 30 W / mK or more. Thereby, gas barrier property and heat dissipation can be imparted to the gas barrier sheet 1A, and as a result, the gas barrier property and heat dissipation that can be used in combination with a heat-generating encapsulated material can be used. The gas barrier sheet 1A having both of the above can be provided. Although details of the exothermic object to be sealed will be described later, any one of an organic EL display element, a liquid crystal display element, and an organic EL lighting element is preferably used. Thereby, the to-be-sealed thing with large exothermic property will be used, and the significance which applies the gas barrier sheet | seat of this invention becomes large. In the present invention, “exothermic object to be sealed” refers to an object that generates heat when the object to be sealed is driven, as the name suggests. Specifically, when the surface temperature of an object to be sealed to be driven is measured and the surface temperature of the object to be encapsulated increases with time, the "exothermic object to be encapsulated" referred to in the present invention Become. For example, when the surface temperature of an object to be sealed is monitored for 24 hours in an environment of normal temperature (25 ± 5 ° C.) and normal humidity (50 ± 10% RH), it is usually 1 ° C. during the measurement time of 24 hours. As described above, the one that rises by 3 ° C. or more, more preferably 5 ° C. or more, is included in the “exothermic sealed object”.

  More specifically, the gas barrier sheet 1 </ b> A has a heat radiating gas barrier film 3 on a base material 2 as shown in FIG. 1.

  Various base materials can be used as the base material 2, and mainly a sheet shape, a film shape, or a take-up roll shape is used. However, depending on a specific application or purpose, a non-flexible substrate is used. Alternatively, a flexible substrate can be used. For example, non-flexible substrates such as glass substrates, hard resin substrates, wafers, printed substrates, various cards, resin sheets, etc. may be used. For example, polyethylene terephthalate (PET), polyamide, polyolefin, polyethylene naphthalate (PEN) Using flexible substrates such as polycarbonate, polyacrylate, polymethacrylate, polyurethane acrylate, polyethersulfone, polyimide, polysilsesquioxane, polynorbornene, polyetherimide, polyarylate, amorphous cyclopolyolefin, cellulose triacetate Also good. In the case where the substrate 2 is made of resin, the resin exemplified above may be appropriately mixed and used as the resin to be used. Moreover, when the base material 2 is resin, what has heat resistance of 100 degreeC or more preferably 150 degreeC or more is suitable suitably.

  As such a resin base material 2, specifically, an amorphous cyclopolyolefin resin film (for example, ZEONEX (registered trademark) or ZEONOR (registered trademark) of Nippon Zeon Co., Ltd., ARTON of JSR Corporation, etc.), Polycarbonate film (for example, Teijin Kasei Co., Ltd. Pure Ace), polyethylene terephthalate film (for example, Teijin Kasei Co., Ltd.), cellulose triacetate film (for example, Konica Minolta Opto Konicakat KC4UX, KC8UX, etc.) And commercially available products such as polyethylene naphthalate film (for example, Teonex (registered trademark) of Teijin DuPont Films Ltd.).

  The thickness of the base material 2 is usually 10 μm or more, preferably 50 μm or more, and usually 200 μm or less, preferably 100 μm or less, from the viewpoints of flexibility and shape retention.

  When the gas barrier sheet 1A including the substrate 2 is provided on the light emitting surface or the image surface side of a display device such as an organic EL display element, the substrate 2 is preferably transparent. By making other films such as the heat dissipating gas barrier film 3 transparent together with the base material 2, the gas barrier sheet 1A can be made transparent. More specifically, for example, it is preferable that the base 2 has an average light transmittance (also referred to as a total light transmittance, the same applies hereinafter) within a range of 400 nm to 700 nm having a transparency of 80% or more. . Since such light transmittance is influenced by the material and thickness of the base material 2, both are considered.

  The surface of the substrate 2 preferably has a predetermined smoothness. Specifically, the arithmetic average roughness (Ra) of the surface of the substrate 2 is usually set to 0.3 nm or more. If it is this range, moderate surface roughness can be provided to the base material 2, and when the base material 2 is used as a take-up roll, slippage hardly occurs on the contact surfaces of the base materials 2 that are in contact with each other. The arithmetic average roughness (Ra) of the surface of the substrate 2 is usually 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. If it is this range, the smoothness of the base material 2 will improve and it will become easy to exhibit the advantage which can suppress the short circuit which may generate | occur | produce when producing display elements, such as an organic EL display. The arithmetic average roughness (Ra) may be measured according to JIS B 0601-2001 (based on ISO 4287-1997).

  It is preferable that the base material 2 is not easily deformed by heat. This is because when the gas barrier sheet 1A is applied to an organic EL display element, the gas barrier sheet 1A is required not to be deformed even by heating / cooling stress such as a heat cycle test. Specifically, the linear expansion coefficient of the base material 2 is usually 5 ppm / ° C. or more, usually 80 ppm / ° C. or less, preferably 50 ppm / ° C. or less. The linear expansion coefficient may be measured using a conventionally known method, for example, a TMA method (thermomechanical analysis method). As a measuring apparatus used for the TMA method, for example, Rigaku CN8098F1 which is a differential expansion type thermomechanical analyzer can be used.

  When a resin-made material is used as the substrate 2, the production method thereof can also be produced by a conventionally known general method. Moreover, when using resin-made base material 2, you may use a stretched film. The stretching method may be a conventionally known general method. Although a draw ratio can be suitably selected according to resin used as the raw material of the base material 2, it is preferable to set it as 2-10 times in a vertical axis direction and a horizontal axis direction, respectively.

  The surface of the substrate 2 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, and the like. As a specific method of such surface treatment, a conventionally known method can be appropriately used. Further, an anchor coat agent film may be formed on the surface of the substrate 2 for the purpose of improving the adhesion with the heat-dissipating gas barrier film 3 or the like. As such an anchor coat agent film, a conventionally known one may be used as appropriate, and details will be described later.

  The heat dissipating gas barrier film 3 is made of diamond-like carbon and has a thermal conductivity of 30 W / mK or more. By using such a heat-dissipating gas barrier film 3, it becomes possible to impart gas barrier properties and heat-dissipating properties to the gas-barrier sheet 1A, and as a result, it can be combined well with exothermic objects to be sealed. Thus, the gas barrier sheet 1A having both gas barrier properties and heat dissipation properties can be provided.

  By configuring the heat dissipating gas barrier film 3 from diamond-like carbon, not only can both heat dissipating properties and gas barrier properties be achieved, it is also easy to ensure the transparency of the gas barrier sheet 1A. That is, when considering both gas barrier properties and heat dissipation properties, it is not unimaginable to use a metal material for the heat dissipation gas barrier film. However, when using a metal material, it becomes difficult to ensure three of heat dissipation, gas barrier property, and transparency simultaneously. This is because when using a metal material, increasing the thickness of the heat-dissipating gas barrier film to ensure the gas barrier property tends to impair transparency, while reducing the thickness of the heat-dissipating gas barrier film to reduce transparency. This is because the gas barrier property is liable to be impaired if the value is secured. On the other hand, when the heat dissipating gas barrier film 3 is made of diamond-like carbon, there is an advantage that it is easy to ensure three of heat dissipating property, gas barrier property, and transparency at the same time.

  Diamond-like carbon (DLC) used as a material for the heat-dissipating gas barrier film 3 refers to a carbon material similar to diamond and has an intermediate crystal structure between diamond and graphite. More specifically, it has an amorphous structure in which carbon is the main component and contains some hydrogen and includes both diamond bonds (SP3 bonds) and graphite bonds (SP2 bonds). Diamond-like carbon is a material that exhibits a predetermined gas barrier property and a predetermined heat dissipation property, and also has an electrical insulating property. For this reason, by using diamond-like carbon, when the gas barrier sheet 1A is used as a display substrate or a sealing film for a display such as an organic EL display element, a short circuit between the cathode and the anode of the display is suppressed. It becomes easy to do.

  The heat dissipating gas barrier film 3 has a thermal conductivity of 30 W / mK or more, preferably 35 W / mK or more, more preferably 40 W / mK or more. By setting the thermal conductivity in the above range, the heat dissipation of the gas barrier sheet 1A is more easily secured. The higher the thermal conductivity, the better the heat dissipation because it is excellent, but it is usually 2000 W / mK or less, which is the thermal conductivity of diamond.

  The thermal conductivity of the heat dissipating gas barrier film 3 can be measured using an optical alternating current method. More specifically, in the present invention, a thermal exchange is measured by using a laser alternating current method thermal diffusivity measuring device Laser PIT-1 manufactured by ULVAC-RIKO, with a diode laser as a heat source and a measurement environment as atmospheric pressure (20 ° C.). did.

  The thermal conductivity of the heat dissipating gas barrier film 3 can be controlled by the composition of diamond-like carbon. Specifically, diamond-like carbon usually contains a predetermined amount of hydrogen, and the heat conductivity of the heat-dissipating gas barrier film 3 may be smaller than 30 W / mK due to this hydrogen. For this reason, in order to control the heat conductivity of the heat-radiating gas barrier film 3 well, it is preferable to adjust the hydrogen content. On the other hand, when an appropriate amount of hydrogen gas is added, there is an advantage that it is easy to ensure the denseness due to the ashing effect.

  The thermal conductivity of the heat-dissipating gas barrier film 3 can also be controlled by adding a predetermined amount of a predetermined additive element to carbon, which is the main component of diamond-like carbon. Examples of such additive elements include silicon (Si), titanium (Ti), aluminum (Al), phosphorus (P), sulfur (S), and chlorine (Cl). Silicon (Si) is preferable from the viewpoint that the bond structure is similar to carbon. It is also effective to add nitrogen (N) or oxygen (O) in order to impart transparency and structural flexibility. From the viewpoint of improving the denseness of the heat dissipating gas barrier film 3, sulfur (S) or chlorine (Cl) is preferable. The content of these additive elements is usually 0 atomic% or more, preferably 0.1 atomic% or more, and usually 4.5 atomic% or less, preferably 2.5 atomic% or less. When Si is used as the additive element, the atomic ratio of carbon (C) and silicon (Si) in the heat-dissipating gas barrier film is C: Si = 1000: 0 to 1000: 40 (Si is at least 0 atomic%) 4 atomic% or less), and preferably C: Si = 1000: 1 to 1000: 20 (Si is 0.1 atomic% or more and 2 atomic% or less). .

  The content of such additive elements can be usually measured by XPS (X-ray photoelectron spectroscopy). In this invention, it measured by XPS (ESCA LAB220i-XL by VG Scientific). As the X-ray source, MgKα ray which is an X-ray source having an Ag-3d-5 / 2 peak intensity of 300 Kcps to 1 Mcps was used, and a slit having a diameter of about 1 mm was used. The measurement was performed with the detector set on the normal line of the sample surface used for the measurement, and appropriate charge correction was performed. The analysis after the measurement uses software Eclipse version 2.1 attached to the above-mentioned XPS apparatus, and Si: 2p, N: 1s, Al: 2p, Mg: 2p, Ti: 2p, P: 2p, O The measurement was performed using peaks corresponding to binding energies of 1 s, C: 1s, S: 2p, and Cl: 2p. At this time, each peak shift was corrected based on the peak corresponding to the hydrocarbon among the C: 1s peaks, and the binding state of the peaks was assigned. For each peak, Shirley background was removed, and the sensitivity coefficient of each element was corrected in the peak area (Si = 0.87, Al = 0.67, Mg = 0.36 with respect to C = 1.0). Ti = 7.90, P = 1.25, N = 1.77, O = 2.85, S = 1.74, Cl = 2.36), and the atomic ratio was determined.

  The thickness of the heat dissipating gas barrier film 3 is usually 2 nm or more, preferably 5 nm or more, and usually 50 nm or less, preferably 30 nm or less. If it is set as the said range, it will become easy to make productivity easy to make a crack with being colorless and transparent, balancing gas barrier property and heat dissipation.

  The extinction coefficient of the heat dissipating gas barrier film 3 is preferably 0.00001 or more and 0.1 or less. The extinction coefficient is preferably as low as possible, but considering productivity, it is more preferably 0.00003 or more, further preferably 0.00005 or more, more preferably 0.07 or less, and still more preferably 0.05 or less. Especially preferably, it is 0.03 or less. Thereby, it becomes easy to ensure the transparency of the heat-dissipating gas barrier film, and as a result, a highly transparent gas barrier sheet 1A can be obtained.

  For the measurement of the extinction coefficient in the heat dissipating gas barrier film 3, a conventionally known method can be used, for example, an ellipsometer can be used. In the present invention, the extinction coefficient was measured by UVISELTM manufactured by JOBIN YVON. The measurement was performed using a xenon lamp as a light source, an incident angle of −60 °, a detection angle of 60 °, and a measurement range of 1.5 eV to 5.0 eV.

  The refractive index of the heat dissipating gas barrier film 3 is usually 1.4 or more, preferably 1.42 or more, more preferably 1.44 or more, and usually 2.2 or less, preferably 2.1 or less, more preferably 2 0 or less. Thereby, it becomes easy to ensure the transparency of the heat-radiating gas barrier film 3, and as a result, a highly transparent gas barrier sheet 1A can be obtained.

  For the measurement of the refractive index in the heat dissipating gas barrier film 3, a conventionally known method can be used, for example, an ellipsometer can be used. In the present invention, the refractive index was measured by UVISELTM manufactured by JOBIN YVON. The measurement was performed using a xenon lamp as a light source, an incident angle of −60 °, a detection angle of 60 °, and a measurement range of 1.5 eV to 5.0 eV.

  The total light transmittance of the gas barrier sheet 1A is usually 60% or more, preferably 70% or more, more preferably 75% or more, and usually 100% or less, preferably 98% or less, more preferably 95% or less. . If it is the said range, transparency of 1 A of gas-barrier sheets can be ensured, and transparency can be made high.

  The total light transmittance of the gas barrier sheet 1A can be measured, for example, using a spectrocolorimeter. In the present invention, the total light transmittance was measured using an SM color computer SM-C (manufactured by Suga Test Instruments). And the measurement was implemented based on JISK7105.

(Method for producing the first aspect of the gas barrier sheet)
The manufacturing method of the gas barrier sheet 1A includes a heat dissipating gas barrier film forming step of forming the heat dissipating gas barrier film 3 made of diamond-like carbon and having a thermal conductivity of 30 W / mK or more. Thereby, it is possible to satisfactorily form the predetermined heat-dissipating gas barrier film 3, and as a result, it is possible to provide a manufacturing method of the gas barrier sheet 1A with high industrial productivity. In addition, the base material preparation process which prepares the base material 2 before a heat radiating gas barrier film formation process can also be implemented. For example, when a resin-made material is used as the substrate 2, as described above, its production method can also be produced by a conventionally known general method, and the production of such a substrate corresponds to the substrate preparation step.

  The heat-dissipating gas barrier film forming step is not particularly limited, and can be performed using, for example, a sputtering method, an ion plating method, a CVD (Chemical Vapor Deposition) method, a plasma CVD method, or the like. Such a manufacturing method may be selected in consideration of the type of film forming material, easiness of film forming, process efficiency, and the like. Some of these manufacturing methods are described below.

  Sputtering is a method in which a target is placed in a vacuum chamber, a noble gas element (usually argon) ionized by applying a high voltage is made to collide with the target, atoms on the target surface are ejected, and attached to the substrate 2. In this method, the heat dissipating gas barrier film 3 is obtained. In the case of forming a diamond-like carbon film, a graphite target is usually used as the target. At this time, a reactive sputtering method in which argon gas or nitrogen gas is allowed to flow into the chamber so that the element ejected from the target adheres to the substrate in an activated state and forms the heat-dissipating gas barrier film 3. May be used. When nitrogen or oxygen is used, the diamond-like carbon film can contain nitrogen or oxygen. When silicon is added, a small amount of organic silicone such as hexamethylenedisiloxane, tetramethoxysilane, tetraethoxysilane, or the like may be added. Examples of the sputtering method include DC dipolar sputtering, RF dipolar sputtering, tripolar and quadrupolar sputtering, ECR sputtering, ion beam sputtering, and magnetron sputtering. Industrially, magnetron sputtering is used. preferable.

  The ion plating method is a combined technique of vacuum vapor deposition and plasma, and is a method of forming a thin film by activating a part of evaporated particles as ions or excited particles using gas plasma in principle. When a diamond-like carbon film is formed, graphite is usually used as a raw material for the evaporated particles. In the ion plating method, argon gas plasma is used to activate the evaporated particles, and a small amount of nitrogen, oxygen, or organic silicone (hexamethylenedisiloxane, tetramethoxysilane, tetraethoxysilane, etc.) is used as the additive gas. Thus, reactive ion plating for synthesizing a diamond-like carbon film is effective. Further, since the operation is in plasma, the first condition is to obtain a stable plasma, and low-temperature plasma by weakly ionized plasma in a low gas pressure region is often used. The ion plating method is roughly classified into a direct current excitation type and a high frequency excitation type from the means for causing discharge, but there are also cases where a holocathode or an ion beam is used for the evaporation mechanism.

  The CVD method refers to a method of forming a film by applying energy to a gas containing a raw material by heat or light, or by generating plasma at a high frequency to radicalize the raw material and adsorb it on a substrate. What is deposited by raising the temperature is called a thermal CVD method, and a method for exciting a gas into a plasma state is called a plasma CVD method. The plasma CVD method will be described later.

  The plasma CVD method is a kind of chemical vapor deposition method. In the plasma CVD method, raw materials are vaporized and supplied during plasma discharge, and the gases in the system are mutually activated and radicalized by collision. Therefore, reactions at low temperatures that are impossible only by thermal excitation are possible. It becomes possible. The substrate 2 is heated from behind by a heater, and a film is formed by a reaction during discharge between the electrodes. It is classified into HF (several tens to hundreds of kHz), RF (13.56 MHz), and microwave (2.45 GHz) depending on the frequency used for generating plasma. When microwaves are used, the method is broadly divided into a method of exciting a reaction gas and forming a film in an afterglow, and an ECR plasma CVD in which microwaves are introduced into a magnetic field (875 Gauss) that satisfies the ECR condition. Further, when classified by the plasma generation method, it is classified into a capacitive coupling method (parallel plate type) and an inductive coupling method (coil method). Here, a holocathode, an ion beam, and an electron beam can be used as the plasma source. Among these, it is preferable to use a holocathode as a plasma source from the viewpoint of generating high-density plasma. More preferably, a pressure gradient type holocathode is used. The diamond-like carbon film is usually formed using a hydrocarbon gas, for example, acetylene, ethylene, methane, or the like. In addition, a hydrogen-containing gas such as hydrogen chloride or hydrogen sulfide can be used as an additive gas when a diamond-like carbon film is formed. By using a hydrogen-containing gas as the additive gas, sulfur and chlorine are mixed into the diamond-like carbon film, and it becomes easy to make it denser, so that it is easier to ensure the heat dissipation of the heat dissipation gas barrier film. On the other hand, when an appropriate amount of hydrogen gas is added, there is an advantage that it is easy to ensure the denseness due to the ashing effect.

  The heat dissipating gas barrier film 3 obtains desired physical properties by appropriately changing the manufacturing conditions while appropriately using the manufacturing method introduced above. Specifically, the thermal conductivity of the heat dissipating gas barrier film 3 can be controlled by the manufacturing method and manufacturing conditions of diamond-like carbon. For example, when reactive sputtering is used, magnetron sputtering is used, and conditions for forming high-density plasma are used. When plasma CVD is used, an MF power source is used to increase the effect of extracting hydrogen from the source gas. When the conditions are employed and the reactive ion plating method is used, it is easy to ensure a predetermined thermal conductivity by employing the conditions for forming a high-density plasma by using a holocathode type plasma gun. By adopting such conditions, the structure of diamond-like carbon becomes dense, and it becomes easy to ensure a predetermined thermal conductivity and gas barrier property.

  When a predetermined amount of an additive element such as silicon is contained in the diamond-like carbon of the heat-dissipating gas barrier film 3 from the viewpoint of thermal conductivity control, for example, a reactive sputtering method or a reactive ion plating method is used. When used, it can be produced by using organic silicone (hexamethylenedisiloxane, tetramethoxysilane, tetraethoxysilane, etc.) as an additive gas, or by mixing a trace amount of silicon with the vapor deposition material. In the case of using the plasma CVD method, it can be manufactured by using organic silicone (hexamethylenedisiloxane, tetramethoxysilane, tetraethoxysilane, or the like) as a reaction gas.

  Furthermore, from the viewpoint of thermal conductivity control, when reducing the hydrogen content in the diamond-like carbon of the heat dissipating gas barrier film 3, for example, when using a reactive sputtering method or a reactive ion plating method, What is necessary is just to produce on conditions with a high degree of vacuum. In the case of using the plasma CVD method, the hydrogen content can be reduced by using a saturated hydrocarbon and using a material having a low hydrogen-carbon bond energy.

  In the present invention, it is preferable that the heat-dissipating gas barrier film forming step is performed by a plasma CVD method using a pressure gradient type holocathode as a plasma source. Thereby, high-density plasma can be generated, and as a result, it becomes easy to ensure the transparency of the heat-dissipating gas barrier film 3. According to the study by the present inventor, when the heat radiation gas barrier film forming step is performed by the plasma CVD method using the pressure gradient type holocathode as the plasma source, the gas injection location and the plasma source, and the heat radiation gas barrier film 3 are formed. It has been found that controlling the distance from the film formation target such as the base material 2 to be filmed is important from the viewpoint of ensuring the transparency of the heat-dissipating gas barrier film 3. Specifically, it has been found that it is important to make the distance longer than the normally set distance (about 30 mm) (for example, about 150 mm, preferably 150 mm or more). The reason for this is unknown, but it is presumed that the activity of the deposited particles by the plasma source decreased in proportion to the distance, and the non-bonded state such as dangling bonds decreased.

(Second aspect of gas barrier sheet)
FIG. 2 is a schematic cross-sectional view showing another example of the gas barrier sheet of the present invention.

  The gas barrier sheet 1D further includes a second gas barrier film 9, and the second gas barrier film 9 contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride. Thereby, it becomes possible to combine the heat-dissipating gas barrier film 3 and the second gas barrier film 9, and it is possible to provide the gas barrier sheet 1D having a higher gas barrier property while maintaining the heat-dissipating property.

  More specifically, as shown in FIG. 2, the gas barrier sheet 1 </ b> D has a second gas barrier film 9 and a heat dissipating gas barrier film 3 in this order on the base material 2. Since the physical property values and the like of the base material 2, the heat dissipating gas barrier film 3, and the gas barrier sheet are as already described, description thereof is omitted here.

The second gas barrier film 9 preferably contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride. By using such a material for the second gas barrier film 9, it becomes easier to secure the gas barrier property of the second gas barrier film 9. The diamond-like carbon used for the heat dissipating gas barrier film 3 usually has a high gas barrier property of about 10 ⁻¹ to 10 ⁻³ g / m ² / day in terms of water vapor transmission rate, but it is desirable to ensure a higher gas barrier property. In this case, the significance of using the second gas barrier film 9 is increased. For example, in an organic EL display element, a gas barrier property of about 10 ⁻⁶ g / m ² / day may be required in terms of water vapor transmission rate. In such a case, it is preferable to use the second gas barrier film 9 in combination. Further, if the second gas barrier film 9 contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride, the second gas barrier film 9 is composed of an inorganic material. Also, the advantage that it is easy to ensure adhesion with the heat-dissipating gas barrier film 3 made of diamond-like carbon is also exhibited.

Silicon nitride used for the second gas barrier film 9 has a composition represented by SiN _a , and a is usually 0.7 or more and 1.4 or less. Further, silicon oxide is a composition represented by SiO _b, b is usually 1.5 or more and 1.8 or less. Further, silicon oxynitride has a composition represented by SiN _c O _d , where c is usually 0.7 or more and 1.2 or less, and d is usually 0.1 or more and 0.5 or less. The composition of the second gas barrier film 9 can be measured by XPS as in the composition analysis of the heat dissipating gas barrier film 3. Specifically, the measurement conditions and data processing conditions may be appropriately adjusted with reference to the method described in the composition analysis of the heat-dissipating gas barrier film 3.

  The content of silicon nitride, silicon oxide, and silicon oxynitride in the second gas barrier film 9 is usually 95 atomic% or more, preferably 99.9 atomic% or more. In addition to silicon nitride, silicon oxide, and silicon oxynitride, the second gas barrier film 9 may contain elements and substances other than Si, N, and O as impurities and additives.

  The thickness of the second gas barrier film 9 is usually 10 nm or more, preferably 20 nm or more, and usually 200 nm or less, preferably 150 nm or less. If it is the said range, while ensuring gas barrier property, transparency will be high and it will become easy to raise productivity with a crack hard to enter.

(Method for producing the second aspect of the gas barrier sheet)
The manufacturing method of the gas barrier sheet 1D may be the same as the manufacturing method of the gas barrier sheet 1A shown in FIG. 1 except that the second gas barrier film forming step of forming the second gas barrier film is performed. It is in. And since the manufacturing method of 1 A of gas-barrier sheets has already been demonstrated, in order to avoid duplication of description, only the said difference is demonstrated below.

  The second gas barrier film forming step can be appropriately performed using a method similar to the method for producing the diamond-like carbon film of the heat dissipating gas barrier film 3. Specifically, for example, a sputtering method, an ion plating method, a Cat-CVD method, a plasma CVD method, or the like may be used. A general description of such a manufacturing method has already been described. Moreover, conventionally well-known knowledge can also be used suitably in such a manufacturing method. When the second gas barrier film 9 is manufactured, for example, in the case of using a sputtering method, by flowing nitrogen gas or oxygen gas in the chamber, the element ejected from the target by the argon gas, and nitrogen or oxygen It is preferable to use a reactive sputtering method in which the heat-dissipating gas barrier film 3 is formed by reacting. Further, for example, when using the ion plating method, it is preferable to use reactive ion plating that combines the vaporized particles using the plasma of the reaction gas to synthesize the compound film.

(Third embodiment of gas barrier sheet)
FIG. 6 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention.

  The gas barrier sheet 1E is formed on the anchor coating agent film 4 provided on the substrate 2, the second gas barrier film 9 provided on the anchor coating agent film 4, and the second gas barrier film 9. The heat-dissipating gas barrier film 3 is provided in this order. As a result, the adhesion between the second gas barrier film 9 and the substrate 2 is ensured, and the flatness of the second gas barrier film 9 and the heat dissipating gas barrier film 3 is easily ensured. A highly gas barrier sheet 1E can be provided.

  The gas barrier sheet 1E adopts the same configuration as the gas barrier sheet 1D shown in FIG. 2 except that the anchor coating agent film 4 is provided between the second gas barrier film 9 and the substrate 2. And since gas barrier sheet | seat sheet | seat 1D was already demonstrated, in order to avoid duplication of description, below, the anchor coat agent film | membrane 4 which is a difference is demonstrated.

  The anchor coat agent film 4 usually functions as an easy-adhesion film. In applications (for example, packaging materials) where it is necessary to improve the adhesion between the substrate 2 and the second gas barrier film 9, it is highly significant to use the anchor coat agent film 4. The anchor coat agent film includes a cardo polymer, a polyfunctional acrylic resin, a layered compound, a silane coupling agent having an organic functional group and a hydrolyzable group, and a second functional group that reacts with the organic functional group of the silane coupling agent. It is preferable to contain at least one of a composition comprising a crosslinkable compound having an organic functional group as a raw material. The thickness of the anchor coat agent film is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 5 μm or less, preferably 1 μm or less.

  Although the gas barrier sheet 1E is not shown in FIG. 6, it is preferable to further provide an antistatic film. As a result, static electricity generated in the organic EL display element and the organic EL lighting element can be easily removed, or dust and dust can be prevented from adhering, and as a result, a gas barrier sheet having higher functionality is provided. be able to. The antistatic film may be provided on the heat dissipating gas barrier film 3 so as to be in contact with an organic EL display element or an organic EL lighting element that is a sealed object that generates static electricity. Moreover, since the antistatic film has a function of preventing dust and dirt from adhering to the antistatic film, it may be provided on the surface of the substrate 2 on which the anchor coating agent film 4 is not provided.

As a material used for the antistatic film, usually, an inorganic material or an organic material can be used, and a material having a predetermined conductivity is preferably used. Examples of the inorganic material (inorganic compound) include ITO, IZO, In ₂ O ₃ , SnO, SnO ₂ , ATO, FTO, ZnO, ZAO, and GZO. On the other hand, examples of the organic material include a PEDOT-PSS mixture. Moreover, the mixture of an inorganic material and an organic material may be sufficient. The thickness of the antistatic film is usually 0.01 μm or more, preferably 0.03 μm or more, and usually 15 μm or less, preferably 10 μm or less.

(Method for producing the third aspect of the gas barrier sheet)
The manufacturing method of the gas barrier sheet 1E may be the same as the manufacturing method of the gas barrier sheet 1D shown in FIG. 2 except that the anchor coating agent film forming step for forming the anchor coating agent film 4 is performed. is there. And since the manufacturing method of gas barrier sheet | seat sheet | seat 1D was already demonstrated, in order to avoid duplication of description, only the said difference is demonstrated below.

  The anchor coating agent film forming step may be appropriately selected according to the material used for the anchor coating agent film 4, and a conventionally known method may be appropriately used. Examples of such a method include a method obtained by applying a coating liquid containing the above-described predetermined material on the substrate 2 and drying and curing the coating solution. Here, examples of the solvent for dissolving or dispersing the predetermined material include alcohol solvents such as methanol, ethanol, and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and methyl acetate; Aromatic hydrocarbon solvents such as toluene and xylene; NMP (N-methylpyrrolidone), glycol diethers, high-boiling solvents such as cyclohexanone, THF (tetrahydrofuran), and the like can be used. What is necessary is just to adjust the solid content concentration of a coating liquid suitably according to the thickness of the anchor coat agent film 4 to obtain.

  When an antistatic film is further provided on the gas barrier sheet 1E, an antistatic film forming step may be further performed. The antistatic film forming step may be appropriately selected according to the material used for the antistatic film, and a conventionally known method may be appropriately used. An example of such a method is a sputtering method. Alternatively, a method of preparing a coating solution by dissolving or dispersing a material used for the antistatic film in a solvent, applying the coating solution, and then drying and curing can be used. Examples of such a coating method include a gravure coating method, a gravure reverse method, and a die coating method.

(Fourth aspect of gas barrier sheet)
FIG. 7 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention.

  In the gas barrier sheet 1F, a third gas barrier film 15 is provided on the surface of the base 2 on which the anchor coating agent film 4 is not provided. Thereby, the 3rd gas barrier film | membrane 15 will be used with the 2nd gas barrier film | membrane 9, As a result, the gas barrier property sheet | seat 1F with higher gas barrier property can be provided.

  The gas barrier sheet 1F adopts the same configuration as the gas barrier sheet 1E shown in FIG. 6 except that the third gas barrier film 15 is provided on the back surface of the substrate 2. Since the gas barrier sheet 1E has already been described, the third gas barrier film 15, which is a difference, will be described below in order to avoid duplication of description. By providing the third gas barrier film 15, the heat dissipating gas barrier film 3, the second gas barrier film 9 and the third gas barrier film 15 can be combined, and the gas barrier property is maintained while maintaining the heat dissipating property. A higher gas barrier sheet 1F can be provided. The third gas barrier film 15 may be the same as the second gas barrier film 9. The second gas barrier film 9 is as already described. Therefore, in order to avoid duplication of explanation, detailed explanation here is omitted.

  Although the gas barrier sheet 1F is not shown in FIG. 7, it is preferable to further provide an antistatic film. As a result, static electricity generated in the organic EL display element and the organic EL lighting element can be easily removed, or dust and dust can be prevented from adhering, and as a result, a gas barrier sheet having higher functionality is provided. be able to. As the antistatic film, the same one as the gas barrier sheet 1E shown in FIG. 6 can be used, and its installation position may be the same. Therefore, in order to avoid duplication of explanation, explanation here is omitted.

(Method for producing the fourth aspect of the gas barrier sheet)
The manufacturing method of the gas barrier sheet 1F may be the same as the manufacturing method of the gas barrier sheet 1E shown in FIG. 6 except that a third gas barrier film forming step for forming the third gas barrier film 15 is performed. In the point. The third gas barrier film forming step, which is a different point, may be performed in the same manner as the second gas barrier film forming step in the method for manufacturing the gas barrier sheet 1D shown in FIG. Therefore, in order to avoid duplication of explanation, explanation here is omitted.

(Layer variation)
As shown in FIG. 1, the gas barrier sheet 1A has a heat dissipating gas barrier film 3 on the substrate 2, and the gas barrier sheet 1D has a second gas barrier film on the substrate 2 as shown in FIG. 9 and the heat-dissipating gas barrier film 3 are provided in this order. As shown in FIG. 6, the gas barrier sheet 1 </ b> E includes a base material 2, an anchor coat agent film 4, a second gas barrier film 9, and a heat dissipating gas barrier film 3 in this order. As shown in FIG. 7, the gas barrier sheet 1F is provided with a third gas barrier film 15 on the surface of the base 2 of the gas barrier sheet 1E on which the anchor coating agent film 4 is not provided. . From the viewpoint of ensuring heat dissipation, the heat dissipating gas barrier film 3 is preferably provided facing the exothermic object to be sealed, and more preferably provided in contact therewith. For this reason, it is preferable that the heat dissipating gas barrier film 3 is disposed on the outermost surface of the gas barrier sheet. As a result, the heat dissipating gas barrier film 3 can be provided on the surface of the exothermic object to be sealed. Furthermore, the heat dissipating gas barrier film 3 can be provided in contact with the surface of the exothermic object to be sealed, so that heat generated from the object to be sealed easily escapes through the heat dissipating gas barrier film 3. This makes it easy to ensure heat dissipation efficiency. As can be seen from the gas barrier sheets 1D, 1E, and 1F, the second gas barrier film 9 is preferably provided in contact with the heat dissipating gas barrier film 3. Thereby, the heat-dissipating gas barrier film 3 and the second gas barrier film 9 are laminated and used, and the gas barrier sheets 1D, 1E, and 1F having higher gas barrier properties are easily obtained.

  However, the layer structure of the gas barrier sheet is not limited to that shown in FIGS. For example, a hard coat film or a smoothing film can be provided on at least one side of the gas barrier sheet. The hard coat film and the smoothing film are usually provided on the surface of the substrate opposite to the surface on which the heat dissipating gas barrier film is provided. Moreover, you may provide an anchor-coat agent film | membrane between a base material and a thermal radiation gas barrier film | membrane. Further, a transparent electrode film may be provided on the heat dissipating gas barrier film. In addition, an antireflection film, the above-described antistatic film, an antifouling layer, and an antiglare layer can be appropriately used as necessary. As such a hard coat film, a smoothing film, an anchor coat agent film, a transparent electrode film, an antireflection film, an antistatic film, an antifouling layer, and an antiglare layer, conventionally known layers may be appropriately used. Thus, the variation regarding the lamination | stacking of a film | membrane can be suitably performed within the range of the summary of this invention.

(First aspect of sealing body)
FIG. 3 is a schematic cross-sectional view showing an example of the sealing body of the present invention.

  The sealing body 10A includes an exothermic sealed object 5 provided on the substrate 7 and a gas barrier sheet 1A provided on the sealed object 5, and at least the gas barrier sheet 1A and the covered object. The surface of the substrate 7 around the sealing material 5 is adhered. The gas barrier sheet 1A has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 is 30 W / mK or more. As a result, the heat-dissipating gas barrier film 3 has both gas barrier properties and heat dissipation properties. As a result, the sealing body 10A capable of ensuring good gas barrier properties and heat dissipation properties with respect to the exothermic sealed object 5 is obtained. Can be offered.

  The board | substrate 7 should just have predetermined | prescribed gas barrier property, supporting the exothermic to-be-sealed thing 5, and there is no restriction | limiting in particular. Examples of such a substrate 7 include a glass substrate and a gas barrier sheet. When the gas barrier sheet is used, the gas barrier sheet of the present invention having a predetermined heat radiating gas barrier film made of diamond-like carbon may be used, or a conventionally known gas barrier sheet may be used. Preferably, the gas barrier sheet of the present invention is used. As a result, the heat dissipating gas barrier films exist above and below the exothermic non-encapsulating body 5, and the heat dissipating characteristics are more easily improved.

  The substrate 7 is preferably transparent when the anode 11 is formed thereon as a transparent electrode. Specifically, for example, it is preferable that the average light transmittance of the substrate 7 in the range of 400 nm to 700 nm has a transparency of 80% or more. More preferably, the average light transmittance is 80% or more in the range of 380 nm to 780 nm.

  The thickness of the substrate 7 is usually 25 μm or more, preferably 50 μm or more, and usually 1 mm or less, preferably 300 μm or less, more preferably 200 μm or less. If it is this range, the mechanical strength of the grade which can support the exothermic to-be-sealed thing 5 can be hold | maintained.

  The exothermic sealed object 5 is an organic EL display element. Since the organic EL display element becomes a sealed object having a large exothermic property, the significance of applying the gas barrier sheet of the present invention is increased. More specifically, the organic EL display element generates heat by generating a part of electric energy when recombining holes and electrons, and has insufficient heat resistance because the element is made of organic matter. It is easy to become. For this reason, in the organic EL display element, it is important to ensure the heat dissipation of the gas barrier sheet 1A. Therefore, it is significant to apply the gas barrier sheet of the present invention having both heat dissipation and gas barrier properties. However, the exothermic sealed object 5 is not limited to the organic EL display element. That is, there is no particular limitation as long as it has exothermic properties, and it is also preferable to use a liquid crystal display element or an organic EL lighting element as the exothermic sealed object. Since the liquid crystal display element and the organic EL lighting element also become a sealed object having a large exothermic property, the significance of applying the gas barrier sheet of the present invention is increased.

  The exothermic sealed object 5 has a normal configuration of an organic EL display element, and includes an anode 11, a hole transport layer 12, a light emitting layer 13, and a cathode 14. A conventionally well-known structure may be appropriately used for each layer.

  The anode 11 only needs to have a function as an electrode for supplying holes to the hole transport layer 12. For this reason, there is no restriction | limiting in particular about the shape of the anode 11, a structure, a magnitude | size, etc., A conventionally well-known material should just be used suitably according to the use and objective of an organic EL display element. Since the anode 11 is often a transparent electrode for the visibility of the display, ITO or IZO is usually used as the material of the anode 11. The anode 11 can be formed by depositing the above material at a predetermined position on the substrate 7 by sputtering or the like. Moreover, you may perform the patterning by an etching as needed. The thickness of the anode 11 is usually set to 140 nm or more and 160 nm or less in consideration of optical interference of the thin film in order to have both transparency and conductivity.

  The hole transport layer 12 has a function of receiving holes from the anode 11 and transporting them to the light emitting layer 13. Such a hole transport layer 12 may contain a conventionally known material having a hole transport function. Examples of such materials include various derivatives such as carbazole derivatives, triazole derivatives, phenylenediamine derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon, Etc. Among these materials, a phenylenediamine derivative is preferable from an industrial point of view, and more specifically, α-naphthylphenyldiamine (α-NPD). Such a hole transport layer 12 can be formed, for example, by forming a film on the anode 11 by a conventionally known production method such as a vacuum deposition method. The thickness of the hole transport layer 12 is usually 1 nm or more and 100 nm or less.

  The light emitting layer 13 has a function of receiving holes from the anode 11 and the hole transport layer 12, receiving electrons from the cathode 14, and providing a field for recombination of holes and electrons to emit light when an electric field is applied. The light emitting layer 13 can be comprised from a conventionally well-known material. For example, the light emitting layer 13 may be composed only of a light emitting material, or may be a mixed layer of a light emitting material and a host material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but the host material is preferably a charge transport material. The host material may be one type or two or more types. When two or more types are used, for example, a configuration in which an electron transporting host material and a hole transporting host material are mixed can be given. Furthermore, the light emitting layer 13 may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer 13 may be one layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of the fluorescent light emitting material used for the light emitting material include various derivatives such as benzoxazole derivatives, aromatic dimethylidin compounds, various metal complexes represented by metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives, polythiophene, Examples include polymer compounds such as polyphenylene and polyphenylene vinylene, and compounds such as organic silane derivatives. Among these materials, a metal complex of 8-quinolinol derivative is preferable from an industrial point of view, and more specifically, tris (8-quinolinol) aluminum (Alq3).

  Examples of the phosphorescent light emitting material used for the light emitting material include complexes containing a transition metal atom or a lanthanoid atom. Examples of the host material include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. Can do.

  The light emitting layer 13 can be formed, for example, by forming a film on the hole transport layer 12 by a vacuum deposition method or the like. The thickness of the light emitting layer 13 is usually 1 nm or more and 100 nm or less.

  The cathode 14 only needs to have a function as an electrode for injecting electrons into the light emitting layer 13. For this reason, there is no restriction | limiting in particular about the shape of the cathode 14, a structure, a magnitude | size, etc., What is necessary is just to use a well-known material suitably according to the use and objective of an organic EL display element.

  The cathode 14 is usually used as a metal electrode. Examples of the material constituting the cathode 14 include metals and alloys. More specifically, examples include metals of Group 2 elements such as Mg and Ca, rare earth metals such as gold, silver, lead, aluminum, indium, lithium-aluminum alloy, magnesium-silver alloy, and ytterbium. Of these materials, aluminum is preferably used. In consideration of stability and electron injection properties, two or more of the above materials may be used in combination. In this case, calcium and silver are preferably used.

  The thickness of the cathode 14 can be appropriately selected depending on the material constituting the cathode 14, and is usually 10 nm or more, preferably 50 nm or more, and usually 5 μm or less, preferably 1 μm or less. The cathode 14 may be transparent or opaque, but when the cathode 14 is transparent, the thickness may be reduced to 1 nm or more and 10 nm or less, or a transparent conductive material such as ITO or IZO may be used. The cathode 14 can be formed by forming a film on the light emitting layer 13 using a vacuum deposition method or the like.

  In addition to the above-described layers, other layers can be added to the organic EL display element of the exothermic sealed object 5 depending on the function required for the organic EL display element. Examples of such a layer include an electron transport layer, a charge blocking layer, and an electron injection layer. Further, a sealing film may be directly provided on the organic EL display element. As the sealing film, an inorganic thin film such as silicon oxide, silicon nitride, or silicon oxynitride is preferably used, and an inorganic thin film of silicon nitride or silicon oxynitride is more preferably used. This is because it is possible to seal lightly and inexpensively than using glass or metal.

  The gas barrier sheet 1A has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 is 30 W / mK or more. As described above for the gas barrier sheet 1A, for example, the atomic ratio of carbon (C) and silicon (Si) in the heat dissipating gas barrier film 3 is C: Si = 1000: 0 to 1000: 40. Is preferred. As a result, as described above, the heat conductivity of the heat-dissipating gas barrier film 3 can be easily set to 30 W / mK or more. A stationary body 10A can be provided. Further, for example, the extinction coefficient of the heat dissipating gas barrier film 3 is preferably set to 0.00001 or more and 0.1 or less. Thereby, as above-mentioned, it becomes easy to ensure the transparency of the heat-radiating gas barrier film 3, and as a result, the sealing body 10A using the highly transparent gas barrier sheet 1A can be provided. The other points are also as already described, and the description here is omitted to avoid duplication of explanation.

  In the sealing body 10A, the cathode 14 and the heat dissipating gas barrier film 3 are provided to face each other. More specifically, the cathode 14 and the heat dissipating gas barrier film 3 are provided in contact with each other. Thereby, the heat generated from the organic EL display element can easily escape through the heat dissipating gas barrier film 3, and as a result, the sealing body 10A with higher heat dissipation efficiency can be provided. Although not shown in FIG. 3, when an exothermic object to be sealed is an organic EL display element, the anode of the organic EL display element and the heat dissipating gas barrier film are provided so as to face each other. Also good. More specifically, the anode and the heat dissipating gas barrier film may be provided in contact with each other. Even with such a configuration, heat generated from the organic EL display element can easily escape via the heat dissipating gas barrier film, and as a result, a sealed body with higher heat dissipation efficiency can be provided.

  The adhesive layer 6 is used for bonding the gas barrier sheet 1A and the surface of the substrate 7 around the exothermic object 5 to be sealed, and is not particularly limited. Examples of the material used for the adhesive layer 6 include a thermosetting resin, a photocurable resin, and an instantaneous adhesive. More specifically, an epoxy resin, an acrylic resin, an acrylonitrile resin, a polyester resin, etc. can be mentioned, for example. Of these materials, it is preferable to use an epoxy resin, an acrylic resin, and an acrylonitrile resin from the viewpoint of low moisture permeability and good heat resistance.

  The adhesive layer 6 is usually a gas barrier sheet after an adhesive having a predetermined viscosity is applied to the periphery of the exothermic object 5 on the surface of the substrate 7 by spin coating, die coating, or the like. It can be formed by coating and curing 1A. The thickness of the adhesive layer 6 is usually 100 nm or more, and usually 1 μm or less, preferably 500 nm or less.

(Second aspect of sealing body)
FIG. 4 is a schematic cross-sectional view showing another example of the sealing body of the present invention.

  The sealing body 10 </ b> D includes the exothermic sealed object 5 provided on the substrate 7 and the gas barrier sheet 1 </ b> D provided on the exothermic sealed object 5, and at least the gas barrier sheet. 1D and the surface of the substrate 7 around the object to be sealed 5 are bonded. The gas barrier sheet 1D has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 is 30 W / mK or more. Further, the gas barrier sheet 1D has a second gas barrier film 9, and the second gas barrier film 9 contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride. Thereby, it becomes possible to combine the heat-dissipating gas barrier film 3 and the second gas barrier film 9, and it is possible to provide the sealing body 10D having a higher gas barrier property while maintaining the heat-dissipating property.

  The sealing body 10D adopts the same configuration as the above-described sealing body 10A except that the gas barrier sheet 1A is changed to the gas barrier sheet 1D. Further, as already described for the gas barrier sheet 1D, the second gas barrier film 9 is provided in contact with the heat dissipating gas barrier film 3. Thereby, the heat-dissipating gas barrier film 3 and the second gas barrier film 9 are stacked and used, and it is possible to provide the sealing body 10D having a higher gas barrier property while maintaining the heat-dissipating property. Since the details of the gas barrier sheet 1D are as described above, the description here is omitted to avoid duplication.

(Third Aspect of Sealing Body)
FIG. 5 is a schematic cross-sectional view showing still another example of the sealing body of the present invention.

  The sealing body 10 </ b> E includes an exothermic sealed object 5 provided on the substrate 7 and a gas barrier sheet 1 </ b> D provided on the sealed object 5. The gas barrier sheet 1D and the surface of the substrate 7 around the object to be sealed 5 are not only bonded via an adhesive layer 8 made of a heat conductive adhesive, but also exothermic to be sealed. The cathode 14 of the organic EL display element used as the object 5 and the heat dissipating gas barrier film 3 are bonded via an adhesive layer 8 made of a heat conductive adhesive.

  In the sealing body 10E, the cathode 14 of the organic EL display element, which is the exothermic sealed object 5, and the heat-dissipating gas barrier film 3 are bonded via an adhesive layer 8 made of a heat conductive adhesive. Therefore, the heat generated from the organic EL display element can easily escape through the adhesive layer 8 made of a heat conductive adhesive and the heat dissipating gas barrier film 3, and as a result, the sealing body having higher heat dissipation efficiency. 10E can be provided.

  The sealing body 10E employs the same configuration as the above-described sealing body 10D except that the adhesive layer 8 made of a heat conductive adhesive is used. For example, the gas barrier sheet 1D has a heat dissipating gas barrier film 3 made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film 3 is 30 W / mK or more. Further, the gas barrier sheet 1D further includes a second gas barrier film 9, and the second gas barrier film 9 contains at least one selected from silicon nitride, silicon oxide, and silicon oxynitride. For this reason, below, the adhesive bond layer 8 which consists of a heat conductive adhesive which is a difference with the sealing body 10D of FIG. 4 is demonstrated.

  The adhesive layer 8 made of a thermally conductive adhesive is not particularly limited as long as it adheres the gas barrier sheet 1D and the exothermic object 5 and has a predetermined thermal conductivity. . The thermal conductivity of the adhesive layer 8 made of a thermally conductive adhesive is usually 0.1 W / mK or higher, preferably 0.15 W / mK or higher, more preferably 0.30 W / mK or higher, and still more preferably 0.8. 50 W / mK or more. On the other hand, the thermal conductivity of the adhesive layer 8 is preferably as high as possible, but is usually 10 W / mK or less because of material limitations and the like.

  Examples of the material used for the adhesive layer 8 made of a thermally conductive adhesive include an epoxy resin, an acrylic resin, an acrylonitrile resin, and a polyester resin. Of these materials, it is preferable to use an epoxy resin, an acrylic resin, and an acrylonitrile resin from the viewpoint of heat dissipation and adhesiveness. In addition, in order to improve thermal conductivity, it is also preferable to add a typical metal, a metal oxide, etc. as an additive in an adhesive agent. Examples of such additives include spherical silica, spherical alumina, and carbon nanotube.

  The adhesive layer 8 made of a heat conductive adhesive is usually an organic EL display that is a surface of the substrate 7 and the exothermic object 5 by spin coating or die coating using an adhesive having a predetermined viscosity. It can be formed by coating the surface of the cathode 14 of the device and the side surface of the organic EL display device, which is the exothermic encapsulating material 5, and then coating and curing the gas barrier sheet 1D. The thickness of the adhesive layer 8 made of a thermally conductive adhesive is usually 50 nm or more, and usually 1 μm or less, preferably 500 nm or less.

  In the sealing body 10E, both the adhesion between the gas barrier sheet 1D and the surface of the substrate 7 around the object to be sealed 5 and the adhesion between the cathode 14 and the heat dissipating gas barrier film 3 (gas barrier sheet 1D) are heated. Although the adhesive layer 8 made of a conductive adhesive is used, the present invention is not limited to such a configuration. For example, another adhesive may be used for bonding the gas barrier sheet 1D and the surface of the substrate 7 around the object 5 to be sealed without considering the thermal conductivity of the adhesive.

  Further, in the sealing body 10E, the cathode 14 and the heat dissipating gas barrier film 3 (gas barrier sheet 1D) are bonded via an adhesive layer 8 made of a heat conductive adhesive. It is not limited to the configuration. For example, the anode of the organic EL display element and the heat dissipating gas barrier film (gas barrier sheet) may be bonded via an adhesive layer made of a heat conductive adhesive. Thereby, the heat generated from the organic EL display element can easily escape via the heat conductive adhesive and the heat dissipating gas barrier film, and as a result, a sealed body with higher heat dissipating efficiency can be provided.

(4th aspect of a sealing body)
FIG. 8 is a schematic cross-sectional view showing still another example of the sealing body of the present invention.

  In the sealing body 10F, the anchor coat agent film 4 provided on the substrate 2, the second gas barrier film 9 provided on the anchor coat agent film 4, and the second gas barrier film 9 are provided. The gas barrier sheet 1E having the heat dissipating gas barrier film 3 provided in this order is used. As a result, the adhesion between the second gas barrier film 9 and the substrate 2 is ensured, and the flatness of the second gas barrier film 9 and the heat dissipating gas barrier film 3 is easily ensured. The sealing body 10F using the gas barrier sheet 1E having high properties can be provided.

  The sealing body 10F adopts the same configuration as the sealing body 10D shown in FIG. 4 except that the gas barrier sheet 1E is used. When the gas barrier sheet 1E is used, for example, although not shown in FIG. 8, it is preferable to further provide an antistatic film on the gas barrier sheet 1E. Thereby, it becomes easy to remove static electricity generated in the organic EL display element (or the organic EL lighting element) which is the exothermic object to be sealed 5 or it is possible to suppress the adhesion of dust and dirt. A sealed body using a gas barrier sheet having higher functionality can be provided. As described above, since the sealing body 10D and the gas barrier sheet 1E are as described above, the description here is omitted to avoid duplication of description.

(5th aspect of a sealing body)
FIG. 9 is a schematic cross-sectional view showing still another example of the sealing body of the present invention.

  In the sealing body 10G, the gas barrier sheet 1F in which the third gas barrier film 15 is provided on the surface of the base material 2 on which the anchor coating agent film 4 is not provided is used. Thereby, the 3rd gas barrier film 15 will be used with the 2nd gas barrier film 9, As a result, the sealing body 10G using the gas barrier property sheet | seat 1F with higher gas barrier property can be provided.

  The sealing body 10G employs the same configuration as the sealing body 10F shown in FIG. 8 except that the gas barrier sheet 1F is used. The gas barrier sheet 1F employs the same configuration as that of the gas barrier sheet 1E shown in FIG. 6 except that the third gas barrier film 15 is provided on the back surface of the substrate 2. For example, the third gas barrier film 15 is provided in the gas barrier sheet 1F. As a result, the heat-dissipating gas barrier film 3 can be combined with the second gas barrier film 9 and the third gas barrier film 15, and the sealing body 10G having a higher gas barrier property while maintaining the heat-dissipating property is provided. can do. Although not shown in FIG. 9, it is preferable to further provide an antistatic film on the gas barrier sheet 1F. Thereby, it becomes easy to remove static electricity generated in the organic EL display element (or the organic EL lighting element) which is the exothermic object to be sealed 5 or it is possible to suppress the adhesion of dust and dirt. A sealed body using a gas barrier sheet having higher functionality can be provided. These points are as described in the gas barrier sheet 1E and the gas barrier sheet 1F. Moreover, it is as having demonstrated the sealing body 10F. Therefore, in order to avoid duplication of explanation, explanation here is omitted.

(Organic EL display)
The organic EL display of the present invention has the sealing body of the present invention. Thereby, an organic EL display element having a large exothermic property is used as an object to be sealed, and an organic EL display capable of ensuring good gas barrier properties and heat dissipation properties can be provided.

  The organic EL display may use conventionally known members, components, devices, etc., except that the above-described sealing body of the present invention is used. Moreover, a conventionally well-known method can be used suitably also about a manufacturing method.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

(Example 1)
A glass substrate having a thickness of 0.7 mm was used as the substrate, and an organic EL display element was used as the exothermic object to be sealed. Specifically, an ITO film was formed on the glass substrate by sputtering, and then patterned by etching to form a transparent electrode (anode). Then, a hole transport layer, a light emitting layer, and a metal electrode (cathode) were sequentially formed on the anode by vapor deposition. Here, α-naphthylphenyldiamine (α-NPD) is used as the material for the hole transport layer, tris (8-quinolinol) aluminum (Alq3) is used as the material for the light emitting layer, and calcium is used as the material for the metal electrode (cathode). And silver were used.

As the gas barrier sheet, a three-layer structure of a base material, a second gas barrier film, and a heat dissipating gas barrier film was used. As the substrate, a polyethylene naphthalate film (Teonex (registered trademark) Q65F, manufactured by Teijin DuPont Films Ltd.) having a thickness of 100 μm was used. Then, on this substrate, a film of silicon nitride by a CVD method to form a second gas barrier film comprising a thickness of 150 nm (a = 1.3 in the composition of the SiN _a). The composition analysis was performed using XPS as in the composition analysis of the heat-dissipating gas barrier film described later. Further, a diamond-like carbon film was formed on the second gas barrier film by an ion plating method to form a heat-dissipating gas barrier film having a thickness of 50 nm.

  The thermal conductivity of the heat-dissipating gas barrier film made of diamond-like carbon film was measured using a laser ACT thermal diffusivity measuring device Laser PIT-1 manufactured by ULVAC-RIKO, with a diode laser as the heat source and the measurement environment at atmospheric pressure ( 20 W), which was 38 W / mK.

  In addition, the composition of the heat dissipating gas barrier film made of diamond-like carbon was measured by XPS (ESCA LAB220i-XL manufactured by VG Scientific). As the X-ray source, MgKα ray which is an X-ray source having an Ag-3d-5 / 2 peak intensity of 300 Kcps to 1 Mcps was used, and a slit having a diameter of about 1 mm was used. The measurement was performed with the detector set on the normal line of the sample surface used for the measurement, and appropriate charge correction was performed. The analysis after the measurement uses software Eclipse version 2.1 attached to the above-mentioned XPS apparatus, and Si: 2p, N: 1s, Al: 2p, Mg: 2p, Ti: 2p, P: 2p, O The measurement was performed using peaks corresponding to binding energies of 1 s, C: 1s, S: 2p, and Cl: 2p. At this time, each peak shift was corrected based on the peak corresponding to the hydrocarbon among the C: 1s peaks, and the binding state of the peaks was assigned. For each peak, Shirley background was removed, and the sensitivity coefficient of each element was corrected in the peak area (Si = 0.87, Al = 0.67, Mg = 0.36 with respect to C = 1.0). Ti = 7.90, P = 1.25, N = 1.77, O = 2.85, S = 1.74, Cl = 2.36), and the atomic ratio was determined. As a result, C was 1 (1000), Si was 0.0 atomic% (0), and N was 0.3 atomic% (3).

  Further, the extinction coefficient and refractive index of the heat dissipating gas barrier film made of diamond-like carbon were measured by UVISELTM manufactured by JOBIN YVON. The measurement was performed using a xenon lamp as a light source, an incident angle of −60 °, a detection angle of 60 °, and a measurement range of 1.5 eV to 5.0 eV. As a result, the heat dissipation gas barrier film had an extinction coefficient of 0.05 and a refractive index of 1.95.

  Next, an adhesive is applied to the substrate surface around the organic EL display element formed on the substrate by a spin coating method so that the heat-dissipating gas barrier film is in contact with the metal electrode (cathode) of the organic EL display element. A gas barrier sheet was placed over the entire organic EL display element. And the gas barrier sheet | seat and the board | substrate surface of the periphery of an organic electroluminescent display element were adhere | attached by hardening an adhesive agent. Here, a UV curable epoxy resin having a thermal conductivity of 0.19 W / mK was used as the adhesive. The sealing body was manufactured through the above.

(Evaluation of luminous characteristics)
As a result of confirming the light emission characteristics of the organic EL display device in an environment of 20 ° C./30% RH with respect to the sealing body thus obtained, the temperature rise of the device surface after continuous light emission for 24 hours was 1 ° C. No spots were generated and good emission characteristics were obtained.

  In addition, the water vapor permeability and oxygen permeability of the gas barrier sheet alone were measured to evaluate the gas barrier properties. Further, the total light transmittance of the gas barrier sheet was measured.

(Measurement of water vapor transmission rate)
The water vapor transmission rate was measured using a water vapor transmission rate measurement apparatus (manufactured by MOCON, USA, PERMATRAN-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 of the water vapor transmission rate measuring apparatus used for the measurement is 0.05 g / m ² · day. As a result of the measurement, the water vapor transmission rate was 0.05 g / m ² · day, which was below the measurement limit value.

(Measurement of oxygen permeability)
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 of the oxygen gas permeability measuring apparatus used for the measurement is 0.05 cc / m ² · day · atm. As a result of the measurement, the oxygen permeability was 0.05 cc / m ² · day · atm, which was below the measurement limit value.

(Measurement of total light transmittance)
The total light transmittance was measured using SM color computer SM-C (manufactured by Suga Test Instruments). And the measurement was implemented based on JISK7105. As a result, the total light transmittance of the gas barrier sheet was 75.3%.

(Example 2)
In Example 1, when bonding the substrate and the gas barrier sheet, not only the surface of the substrate around the organic EL display element formed on the substrate but also the metal electrode (cathode) of the organic EL display element, and the organic An encapsulant was manufactured in the same manner as in Example 1 except that an adhesive was also applied to the side surface of the EL display element to further bond the metal electrode (cathode) and the heat dissipating gas barrier film.

  With respect to the sealing body thus obtained, the light emission characteristics of the organic EL display element were confirmed in an environment of 20 ° C./30% RH. As a result, the temperature rise of the element surface after continuous light emission for 24 hours was 0 ° C. No spots were generated and good emission characteristics were obtained.

(Example 3)
A sealing body was manufactured in the same manner as in Example 1 except that a heat-dissipating gas barrier film was formed by a plasma CVD method (PECVD method) on the gas barrier sheet and the thickness thereof was 30 nm. The thermal conductivity of the deposited heat-dissipating gas barrier film was measured in the same manner as in Example 1 and found to be 35 W / mK. Further, the composition of the heat dissipating gas barrier film made of diamond-like carbon was measured in the same manner as in Example 1. As a result, C was 1 (1000) and Si was 0.1 atomic% (1).

  The measurement conditions of the plasma CVD method are a pressure gradient type holocathode plasma gun as the plasma source, and the distance between the substrate, which is the deposition target, and the second gas barrier film, the gas injection location, and the plasma source. Was set to 150 mm. Other conditions were Ar flow rate: 20 sccm, ethylene gas: 50 sccm.

  When the extinction coefficient and refractive index of the heat-dissipating gas barrier film made of diamond-like carbon were measured in the same manner as in Example 1, the extinction coefficient was 0.012 and the refractive index was 1.59.

  As a result of confirming the light emission characteristics of the organic EL display device in an environment of 20 ° C./30% RH with respect to the sealing body thus obtained, the temperature rise of the device surface after continuous light emission for 24 hours was 1 ° C. No spots were generated and good emission characteristics were obtained.

Further, the water vapor transmission rate and oxygen transmission rate of the gas barrier sheet were measured in the same manner as in Example 1. As a result, water vapor transmission rate was 0.05g ^/ m 2 · day, the oxygen permeability is ^{0.05cc / m 2 · day · atm} , were all below the detectable limit.

  When the total light transmittance of the gas barrier sheet was measured in the same manner as in Example 1, the total light transmittance was 90.0%.

Example 4
In the gas barrier sheet, a heat-dissipating gas barrier film was formed by the plasma CVD method (PECVD method), and the thickness thereof was set to 30 nm (the same content as in Example 3). Thus, a sealing body was manufactured.

  With respect to the sealing body thus obtained, the light emission characteristics of the organic EL display element were confirmed in an environment of 20 ° C./30% RH. As a result, the temperature rise of the element surface after continuous light emission for 24 hours was 0 ° C. No spots were generated and good emission characteristics were obtained.

(Example 5)
In the gas barrier sheet, except that the material of the second gas barrier film was silicon oxynitride, the heat-dissipating gas barrier film was formed by plasma CVD (PECVD method), and the thickness thereof was 20 nm. 1 was produced in the same manner as in Example 1.

  The measurement conditions of the plasma CVD method are as follows: an RF power source is used as a plasma source, and the distance between the stack of the base material to be deposited and the second gas barrier film, the gas injection location, and the plasma source is 40 mm. Set. Other conditions were Ar flow rate: 20 sccm, ethylene gas: 50 sccm, hydrogen gas: 10 sccm, HMDSO: 3 sccm, nitrogen gas: 5 sccm. Here, HMDSO refers to hexamethylene disiloxane.

The composition of the second gas barrier film was measured in the same manner as in Example 1. As a result, c = 1.0 and d = 0.4 for SiN _c O _d . Further, the thermal conductivity of the deposited heat-dissipating gas barrier film was measured in the same manner as in Example 1, and found to be 35 W / mK. The composition of the heat-dissipating gas barrier film made of diamond-like carbon was measured in the same manner as in Example 1. As a result, C was 1 (1000), Si was 0.1 atomic% (1), and N was 0.00. It was 2 atomic% (2).

  Furthermore, when the extinction coefficient and refractive index of the heat dissipating gas barrier film made of diamond-like carbon were measured in the same manner as in Example 1, the extinction coefficient was 0.01 and the refractive index was 1.59.

  As a result of confirming the light emission characteristics of the organic EL display device in an environment of 20 ° C./30% RH with respect to the sealing body thus obtained, the temperature rise of the device surface after continuous light emission for 24 hours was 1 ° C. No spots were generated and good emission characteristics were obtained.

Further, the water vapor transmission rate and oxygen transmission rate of the gas barrier sheet were measured in the same manner as in Example 1. As a result, water vapor transmission rate was 0.05g ^/ m 2 · day, the oxygen permeability is ^{0.05cc / m 2 · day · atm} , were all below the detectable limit.

  When the total light transmittance of the gas barrier sheet was measured in the same manner as in Example 1, the total light transmittance was 81.1%.

(Example 6)
In the gas barrier sheet, the material of the second gas barrier film was silicon oxynitride, and the heat-dissipating gas barrier film was formed by the plasma CVD method (PECVD method), and the thickness thereof was set to 20 nm (Example 5 and A sealed body was manufactured in the same manner as in Example 2 except that the contents were the same.

The composition of the second gas barrier film was measured in the same manner as in Example 1. As a result, c = 1.1 and d = 0.1 for SiN _c O _d .

  With respect to the sealing body thus obtained, the light emission characteristics of the organic EL display element were confirmed in an environment of 20 ° C./30% RH. As a result, the temperature rise of the element surface after continuous light emission for 24 hours was 0 ° C. No spots were generated and good emission characteristics were obtained.

(Comparative Example 1)
In Example 1, the second gas barrier film was not used, and the thermal conductivity of the heat dissipating gas barrier film was increased to 20 W / mK by increasing the concentration of argon gas in the ion plating method when forming the heat dissipating gas barrier film. A sealed body was manufactured in the same manner as in Example 1 except that the following was achieved. The composition of the heat-dissipating gas barrier film made of diamond-like carbon was measured in the same manner as in Example 1. As a result, C was 1 (1000), Si was 0.5 atom% (5), and N was 0.4 atom. % (4).

  Furthermore, when the extinction coefficient and refractive index of the heat dissipating gas barrier film made of diamond-like carbon were measured in the same manner as in Example 1, the extinction coefficient was 0.07 and the refractive index was 1.94.

  As a result of confirming the light emission characteristics of the organic EL display device in an environment of 20 ° C./30% RH with respect to the sealing body thus obtained, the temperature rise of the device surface after continuous light emission for 24 hours was 5 ° C., which was dark. Spots were generated and the light emission characteristics were poor.

Further, the water vapor transmission rate and oxygen transmission rate of the gas barrier sheet were measured in the same manner as in Example 1. As a result, the water vapor transmission rate was 0.1 g / m ² · day, and the oxygen transmission rate was 0.2 cc / m ² · day · atm. This is presumed that the structure of the heat-dissipating gas barrier film becomes porous and the desired thermal conductivity cannot be obtained, and the gas barrier property is also lowered due to the porous nature.

  When the total light transmittance of the gas barrier sheet was measured in the same manner as in Example 1, the total light transmittance was 57.3%.

It is a typical sectional view showing an example of the gas barrier sheet of the present invention. It is typical sectional drawing which shows another example of the gas barrier sheet | seat of this invention. It is typical sectional drawing which shows an example of the sealing body of this invention. It is typical sectional drawing which shows another example of the sealing body of this invention. It is typical sectional drawing which shows another example of the sealing body of this invention. It is typical sectional drawing which shows another example of the gas barrier sheet | seat of this invention. It is typical sectional drawing which shows another example of the gas barrier sheet | seat of this invention. It is typical sectional drawing which shows another example of the sealing body of this invention. It is typical sectional drawing which shows another example of the sealing body of this invention.

Explanation of symbols

1, 1A, 1D, 1E, 1F Gas barrier sheet 2 Base material 3 Heat dissipating gas barrier film 4 Anchor coat agent film 5 Exothermic sealed object (organic EL display element)
6 Adhesive Layer 7 Substrate 8 Adhesive Layer Made of Thermally Conductive Adhesive 9 Second Gas Barrier Film 10, 10A, 10D, 10E, 10F, 10G Sealing Body 11 Anode 12 Hole Transport Layer 13 Light-Emitting Layer 14 Cathode 15 Third gas barrier film

Claims (15)

A gas barrier sheet for sealing exothermic objects to be sealed,
The gas barrier sheet has a heat dissipating gas barrier film made of diamond-like carbon, and the heat conductivity of the heat dissipating gas barrier film is 30 W / mK or more.   The gas barrier sheet according to claim 1, wherein an atomic ratio of carbon (C) and silicon (Si) in the heat dissipation gas barrier film is C: Si = 1000: 0 to 1000: 40.   The gas barrier sheet further includes a second gas barrier film and / or a third gas barrier film, and the second gas barrier film and the third gas barrier film are made of silicon nitride, silicon oxide, and silicon oxynitride, respectively. The gas barrier sheet according to claim 1 or 2, comprising at least one selected.   The gas barrier sheet according to claim 3, wherein the second gas barrier film is provided in contact with the heat dissipating gas barrier film.   The gas barrier sheet according to any one of claims 1 to 4, wherein the exothermic object to be sealed is any one of an organic EL display element, a liquid crystal display element, and an organic EL lighting element.   The gas barrier sheet according to any one of claims 1 to 5, wherein an extinction coefficient of the heat dissipating gas barrier film is 0.00001 or more and 0.1 or less.   An anchor coating agent film provided on a substrate, the second gas barrier film provided on the anchor coating agent film, and the heat dissipating gas barrier film provided on the second gas barrier film The gas barrier sheet according to any one of claims 3 to 6, wherein   The gas barrier sheet according to claim 7, wherein the third gas barrier film is provided on a surface of the substrate on which the anchor coating agent film is not provided.   The gas barrier sheet according to claim 7 or 8, further comprising an antistatic film.   The method for producing a gas barrier sheet according to any one of claims 1 to 9, wherein the heat dissipative gas barrier film is formed of diamond-like carbon and has a heat conductivity of 30 W / mK or more. A method for producing a gas barrier sheet, comprising a forming step.   The method for producing a gas barrier sheet according to claim 10, wherein the heat dissipating gas barrier film forming step is performed by a plasma CVD method using a pressure gradient type holocathode as a plasma source.   An exothermic sealed object provided on a substrate, and the gas barrier sheet according to claim 1 provided on the sealed object, and at least the gas barrier The sealing body characterized by the adhesive sheet and the said substrate surface of the said to-be-sealed thing periphery being adhere | attached.   The sealing body according to claim 12, wherein the exothermic object to be sealed is an organic EL display element, and a cathode or an anode of the organic EL display element and the heat dissipating gas barrier film are provided to face each other. .   The sealing body according to claim 13, wherein the cathode or anode of the organic EL display element and the heat dissipating gas barrier film are bonded via a heat conductive adhesive.   An organic EL display comprising the sealing body according to any one of claims 12 to 14.

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