JP5223540B2 - Gas barrier sheet and method for producing gas barrier sheet - Google Patents

Description

  The present invention relates to a gas barrier sheet and a method for producing the same, and more particularly to a gas barrier sheet having excellent transparency, high heat resistance, hardly curling, excellent hard coat properties, and excellent gas barrier properties, and a method for producing the same. .

  Attempts have been made in the past to develop a high gas barrier property by forming an inorganic or organic thin film on a substrate film.

  Patent Document 1 includes a cured product of a UV curable resin containing only an acrylic monomer and / or an acrylic polymerizable prepolymer as a polymerization component from one side or both surfaces of a flexible base material from the side close to the base material. A gas barrier film having a laminated structure in which an acrylic resin layer having a thickness of 0.1 to 10 μm and an inorganic barrier layer having a thickness of 20 to 100 nm are sequentially laminated is introduced.

According to the document, a UV curable resin layer having a specific thickness is directly formed on a flexible substrate using the specific UV curable resin, and an inorganic barrier layer having a specific thickness is further formed thereon. When the film is laminated, a gas barrier film can be obtained which exhibits good gas barrier properties and hardly causes curling in the production process. Then, as the ceramic material used for the inorganic barrier _{layer, SiO x, AlO x, SiO} x N y, SiN x, SiO x N y C z, SiN x C y, AlO x N y, AlN x, AlO x N y C _z, and _AlN x _{C y} and the like are exemplified.

Patent Document 2 introduces a surface-treated resin molded body obtained by treating at least one surface of a resin molded body with a predetermined surface treatment composition. And the said composition for surface treatment has in the molecule | numerator the functional group which can react with the organic group (A) for providing flexibility to the film formed, and the amino group in this organic compound (A). A compound (B), a predetermined organometallic compound (C), and a solvent (D) are contained. Specifically, polyethyleneimine as the organic compound (A), γ-glycidoxypropyltrimethoxysilane as the compound (B), tetramethoxysilane as the compound (C), and methanol as the solvent (D) are used in Example 1. It has been.
Japanese Patent Laying-Open No. 2005-313560 (Claim 1, Paragraph 0012, Paragraph 0039) JP-A-8-295848 (Claims 1, 7, 0008, 0011, 0015, 0030)

  In Patent Document 1, by combining an acrylic resin film having a specific thickness and a gas barrier film having a specific thickness made of an inorganic material, both the gas barrier property of the gas barrier sheet and the suppression of curling are achieved. ing.

  However, in the gas barrier sheet described in the same document, an acrylic resin is used when heat treatment is performed under more severe conditions in the post-production process for the purpose of producing a multilayer structure or performing an annealing process. The film is heated and easily yellows. And since the gas barrier sheet is colored by yellowing of the acrylic resin film, the gas barrier sheet described in the same document has a problem in heat resistance when viewed on a stricter standard. .

  In addition, a surface-treated resin molded body in which at least one surface of a resin molded body in Patent Document 2 is treated with a predetermined surface treatment composition (hereinafter, the surface-treated resin molded body is referred to as a “gas barrier sheet”) is a gas barrier. As a result, it has been found that the present invention still has problems in suppressing the generation of curling, transparency, heat resistance, and curling.

That is, when a liquid crystal display, an organic EL display, or the like is considered as a gas barrier sheet, the water vapor transmission rate is usually 0.1 g / m ² / day (g / m ² · day) or less and the oxygen transmission rate is low. It is required to have a high gas barrier property of 0.1 cc / m ² / day · atm (cc / m ² · day · atm) or less. However, as shown in the Examples of Patent Document 2, the gas barrier sheet of Patent Document 2 cannot achieve such a high gas barrier property.

  Moreover, when an organic EL display etc. are considered as a use of a gas barrier sheet | seat, it is desired to make transparency of a gas barrier sheet | seat high. However, in Patent Document 2, since the organic compound (A) is used to impart flexibility to the formed film, the organic functional group in the film increases and light absorption is likely to occur in the visible light region. Become. As a result, the transparency of the gas barrier sheet tends to decrease. For this reason, there is a problem in transparency.

  Furthermore, since many organic functional groups are present in the film due to the organic compound (A), the gas barrier sheet is easily colored by the temperature load, and there is a problem in heat resistance.

  In addition, when an organic EL display or the like is considered as an application of the gas barrier sheet, it is desired to suppress deformation (curl) of the gas barrier sheet during holding at a high temperature in the manufacturing process. However, in Patent Document 2, since the organic compound (A) is used to impart flexibility to the film to be formed, the organic functional group in the film increases and the film stress increases, so that the curve is increased. It tends to occur. For this reason, there is also a problem from the viewpoint of curling suppression.

  The present invention has been made in order to solve the above-mentioned problems, and its object is to provide a gas barrier sheet having excellent transparency, high heat resistance, hardly curling, and excellent gas barrier properties. . Furthermore, it is providing the gas barrier property sheet | seat which is excellent also in hard-coat property. In particular, an object of the present invention is to provide a gas barrier sheet in which the occurrence of curling is suppressed and the gas barrier performance is maintained even after a heat cycle test performed as a durability test for an organic EL display or the like.

  The present inventor uses a polysiloxane polymer for the anchor film and controls the structure of the polysiloxane polymer to obtain a gas barrier sheet having high heat resistance, excellent transparency, and a predetermined stiffness. I found out that I can. Since the gas barrier sheet can be imparted with an appropriate hardness, it is difficult to curl even when there is a temperature load, and the hard coat property is easily improved. By providing a gas barrier film of silicon oxynitride having a predetermined composition on the anchor film, a gas barrier function can be ensured by two layers of the anchor film and the gas barrier film, and a high level gas barrier is achieved. We found that sex can be achieved. Furthermore, when the base material, the anchor film, and the gas barrier film are provided in contact with each other, the affinity between Si in the gas barrier film and Si in the anchor film is high, and Si—C bonds are in contact with the base material. It was found that the adhesion of the substrate, the anchor film, and the gas barrier film can be increased in order to improve the adhesion of the substrate. In particular, a gas barrier sheet having high gas barrier properties required for an organic EL display and curling can be suppressed and gas barrier performance can be maintained even through a heat cycle test performed as a durability test of the organic EL display is obtained. I found out.

The gas barrier sheet of the present invention for solving the above problems comprises a base material, an anchor film provided on one side of the base material, and a gas barrier film provided on the anchor film. In the gas barrier sheet having, the anchor film contains a polysiloxane polymer composed of a siloxane compound and a compound A having a functional group capable of reacting with a hydroxyl group of the siloxane compound at the time of polymerization. The gas barrier film is a SiN _x O _y film (where x = 0.5 to 1.5, y = 0.15 to 1).

According to this invention, the anchor film contains a polysiloxane polymer composed of a siloxane compound and a compound A having a functional group in the molecule that can react with a hydroxyl group of the siloxane compound at the time of polymerization. Since the film is a SiN _x O _y film (x = 0.5 to 1.5, y = 0.15 to 1), the structure of the polysiloxane polymer is controlled, and the transparency and heat resistance of the anchor film are controlled. Property and hardness can be controlled, and the gas barrier property can be secured with two layers of the anchor film and the gas barrier film, and further, when the base material, the anchor film, and the gas barrier film are provided in contact with each other, The interaction between the anchor film and the gas barrier film is enhanced by Si in the anchor film and Si in the gas barrier film, and the Si—C bond in the anchor film improves the interaction with the substrate. As a result, it is possible to provide a gas barrier sheet that is excellent in transparency, high in heat resistance, difficult to curl, excellent in hard coat properties, excellent in gas barrier properties, and also excellent in adhesiveness.

  In a preferred embodiment of the gas barrier sheet of the present invention, the polysiloxane polymer is composed of 70 mol% to 99 mol% of the siloxane compound and 1 mol% to 30 mol% of the compound A.

  According to this invention, since the polysiloxane polymer is composed of 70 mol% to 99 mol% of the siloxane compound and 1 mol% to 30 mol% of the compound A, the structure of the polysiloxane polymer is controlled and the anchor film As a result, it is possible to adjust the transparency, heat resistance, and hardness of the gas barrier sheet with excellent transparency, high heat resistance, resistance to curling, and excellent hard coat properties. It becomes easier to provide.

  In another preferred embodiment of the gas barrier sheet of the present invention, the anchor film has an extinction coefficient of 0.00001 to 0.01.

  According to this invention, since the extinction coefficient of the anchor film is 0.00001 to 0.01, it becomes easy to ensure the transparency of the anchor film. As a result, the gas barrier sheet having excellent transparency is provided more. It becomes easy.

  In another preferable aspect of the gas barrier sheet of the present invention, the extinction coefficient of the gas barrier film is 0.000001 to 0.01.

  According to this invention, since the extinction coefficient of the gas barrier film is 0.000001 to 0.01, it is easy to ensure the transparency of the gas barrier film, and as a result, a gas barrier sheet having excellent transparency is provided more. It becomes easy.

  In another preferable aspect of the gas barrier sheet of the present invention, the anchor film is provided also on the other surface side of the base material, and the gas barrier film is provided on the anchor film.

  According to this invention, the anchor film (second anchor film) is provided also on the other surface side of the base material, and the gas barrier film (second gas barrier film) is provided on the anchor film. Since the anchor film and the gas barrier film are provided on both sides, the gas barrier property and hardness can be further increased. As a result, a gas barrier sheet that is difficult to curl, has excellent hard coat properties, and has excellent gas barrier properties. It becomes easier to provide.

  In another preferred embodiment of the gas barrier sheet of the present invention, a transparent conductive film is provided on the gas barrier film.

  According to this invention, since the transparent conductive film is provided on the gas barrier film, the transparent conductive film can be used as an anode of an organic EL display, or a heat dissipation function and an antistatic function can be imparted to the gas barrier sheet. By providing the transparent conductive film, it becomes easy to improve the productivity and life of the organic EL display.

  In another preferred embodiment of the gas barrier sheet of the present invention, a hard coat film is provided on at least one side of the gas barrier sheet.

  According to the present invention, since the hard coat film is provided on at least one side of the gas barrier sheet, the gas barrier sheet is protected by the hard coat film, and as a result, it is easier to provide a gas barrier sheet that is not easily damaged. Become.

  In another preferred embodiment of the gas barrier sheet of the present invention, the gas barrier film is formed by aggregation of secondary particles, and the particle size of the secondary particles is 300 nm or more and 1500 nm or less.

  According to the present invention, since the gas barrier film is formed by the aggregation of the secondary particles and the particle size of the secondary particles is 300 nm or more and 1500 nm or less, the adjacent secondary particles are sufficiently aggregated. The gas barrier property can be secured without reducing the productivity while maintaining the flexibility.

  In another preferable aspect of the gas barrier sheet of the present invention, the distance between the adjacent secondary particles is 100 nm or more and 300 nm or less.

  According to this invention, since the distance between adjacent secondary particles is 100 nm or more and 300 nm or less, aggregation of adjacent secondary particles is promoted, and as a result, the flexibility of the base material is more easily maintained. A gas barrier sheet can be provided.

  In another preferred embodiment of the gas barrier sheet of the present invention, a moisture absorbing film formed of a material B that can adsorb and desorb moisture and can maintain a solid state even when moisture is adsorbed is further provided.

  According to the present invention, since the moisture absorbing film formed of the material B that can absorb and desorb moisture and can maintain a solid state even when moisture is adsorbed is provided, the moisture absorption becomes a reversible moisture absorbing film. As a result, it is possible to provide a gas barrier sheet capable of maximizing moisture absorption performance by subjecting the gas barrier sheet of the present invention to a heating step before use.

  In another preferable aspect of the gas barrier sheet of the present invention, the material B is an alkali metal oxide or an alkaline earth metal oxide.

  According to this invention, since the material B is an alkali metal oxide or an alkaline earth metal oxide, the material B having good moisture absorption characteristics is used for the moisture absorption film. As a result, the moisture absorption film having high moisture absorption characteristics is used. The gas barrier sheet | seat which has can be provided.

In another preferable aspect of the gas barrier sheet of the present invention, the moisture absorption film has an extinction coefficient of 1 × 10 ⁻⁶ to 1 × 10 ⁻³ .

According to this invention, since the extinction coefficient of the hygroscopic film is 1 × 10 ⁻⁶ to 1 × 10 ⁻³ , it becomes easy to ensure the transparency of the hygroscopic film, and as a result, the gas barrier sheet having excellent transparency. It will be easier to provide.

  In another preferred embodiment of the gas barrier sheet of the present invention, a heat dissipating gas barrier film is further provided.

  According to this invention, since the heat-dissipating gas barrier film is further provided, even when the object to be sealed sealed with the gas barrier sheet of the present invention is exothermic, the heat dissipation can be performed satisfactorily. As a result, it becomes easy to provide a gas barrier sheet that not only has excellent gas barrier properties but also has excellent heat dissipation properties.

  The method for producing a gas barrier sheet of the present invention for solving the above problems is obtained by polymerizing a siloxane compound and a compound A having a functional group in the molecule that can react with a hydroxyl group of the siloxane compound during polymerization. And an anchor film forming step for forming an anchor film using the polysiloxane polymer, and a gas barrier film forming step for forming a gas barrier film.

  According to this invention, an anchor film is formed using a polysiloxane polymer obtained by polymerizing a siloxane compound and a compound A having a functional group capable of reacting with a hydroxyl group of the siloxane compound during polymerization. Since it has an anchor film forming step for forming a film and a gas barrier film forming step for forming a gas barrier film, the gas barrier sheet of the present invention can be manufactured satisfactorily, and as a result, various characteristics such as gas barrier properties The manufacturing method of the gas-barrier sheet | seat excellent in can be provided.

  According to the gas barrier sheet of the present invention, it is possible to provide a gas barrier sheet that is excellent in transparency, has high heat resistance, is difficult to curl, and has excellent gas barrier properties. Furthermore, a gas barrier sheet having excellent hard coat properties can be provided.

  According to the method for producing a gas barrier sheet of the present invention, it is possible to provide a method for producing a gas barrier sheet that can satisfactorily produce the gas barrier sheet of the present invention having excellent various characteristics.

  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.

  FIG. 1 is a schematic sectional view showing an example of the gas barrier sheet of the present invention, FIG. 2 is a schematic sectional view showing another example of the gas barrier sheet of the present invention, and FIG. FIG. 4 is a schematic cross-sectional view showing still another example of the gas barrier sheet, and FIG. 4 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention. FIG. 6 is a schematic sectional view showing still another example of the gas barrier sheet of the present invention, and FIG. 7 is a schematic sectional view showing still another example of the gas barrier sheet of the present invention. is there. FIG. 8 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention. FIG. 9 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention. FIG. 10 is a schematic cross-sectional view showing still another example of the gas barrier sheet of the present invention.

  As shown in FIG. 1, the gas barrier sheet 1 of the present invention includes a base material 2, an anchor film 9A provided on one surface 11 side of the base material 2, and a gas barrier provided on the anchor film 9A. And a gas barrier sheet 1A having a film 3A. Although details will be described later, by using the form of the gas barrier sheet 1A, the structure of the polysiloxane polymer is controlled to control the transparency, heat resistance, and rigidity of the anchor film 9A. Gas barrier properties can be ensured with two layers of 3A. Further, since the substrate 2, the anchor film 9A, and the gas barrier film 3A are provided in contact with each other, the interaction between the anchor film 9A and the gas barrier film 3A is caused by Si in the anchor film 9A and Si in the gas barrier film 3A. And the Si—C bond in the anchor film 9A improves the interaction with the substrate 2. As a result, it is possible to provide a gas barrier sheet 1A that is excellent in transparency, high heat resistance, difficult to curl, excellent in hard coat properties, excellent in gas barrier properties, and in addition, excellent in adhesiveness.

  As shown in FIG. 2, the gas barrier sheet 1 of the present invention includes a base material 2, an anchor film 9A provided on one surface 11 side of the base material 2, and a gas barrier provided on the anchor film 9A. It can also have the form of gas barrier sheet 1B which has film 3A and transparent conductive film 4 provided on gas barrier film 3A. Although details will be described later, the transparent conductive film 4 can be used as an anode of an organic EL display, or a heat dissipation function and an antistatic function can be imparted to the gas barrier sheet 1B. Thus, it becomes easy to improve the productivity and life of the organic EL display.

  As shown in FIG. 3, the gas barrier sheet 1 of the present invention may have a form in which a hard coat film 5 is provided on at least one surface of the gas barrier sheet 1C. More specifically, the gas barrier sheet 1C has an anchor film 9A and a gas barrier film 3A in this order on one surface 11 of the substrate 2, and the other surface 12 of the substrate 2, that is, the substrate The hard coat film 5 is provided on the opposite surface of the two surfaces to the surface on which the anchor film 9A is formed. As will be described in detail later, since the hard coat film 5 is provided on at least one side of the gas barrier sheet 1C, the gas barrier sheet 1C is protected by the hard coat film 5, and as a result, the gas barrier is less likely to be damaged. It becomes easier to provide the adhesive sheet 1C.

  As shown in FIG. 4, the gas barrier sheet 1 of the present invention is provided with an anchor film 9B (second anchor film) also on the other surface 12 side of the substrate 2, and the gas barrier film 3B is formed on the anchor film 9B. It can also have the form of gas barrier sheet 1D which provides (2nd gas barrier film). Since the anchor films 9A and 9B and the gas barrier films 3A and 3B are provided so as to sandwich the base material 2, the anchor films 9A and 9B and the gas barrier films 3A and 3B are provided on both surfaces of the base material. For this reason, gas barrier property and firmness can be made higher, and as a result, it becomes easier to provide a gas barrier sheet 1D that is less likely to curl, has excellent hard coat properties, and has excellent gas barrier properties.

  As shown in FIG. 6, the gas barrier sheet 1 of the present invention has a gas barrier sheet 1 </ b> E configuration in which a gas barrier film 3 </ b> C is provided on the other surface 12 side of the substrate and a transparent conductive film 4 is provided on the gas barrier film 3 </ b> C. Can also be included. More specifically, in the gas barrier sheet 1E, the anchor film 9B is provided on the one surface 11 side of the base material 2, the gas barrier film 3B is provided on the anchor film 9B, and the other surface 12 side of the base material is provided. A gas barrier film 3C is provided, and a transparent conductive film 4 is provided on the gas barrier film 3C.

  As shown in FIG. 7, the gas barrier sheet 1 of the present invention is the surface on which the anchor film 9 </ b> A, the gas barrier film 3 </ b> A, and the transparent conductive film 4 are not provided, of both surfaces of the base material 2 of the gas barrier sheet 1 </ b> B. A gas barrier sheet 1F may be provided in which a gas barrier film 3D is provided. More specifically, the gas barrier sheet 1 </ b> F is provided with an anchor film 9 </ b> A, a gas barrier film 3 </ b> A, and a transparent conductive film 4 in this order on one surface side of the substrate 2, and a gas barrier on the other surface of the substrate 2. A film 3D is provided.

  As shown in FIG. 8, the gas barrier sheet 1 of the present invention can absorb and desorb moisture in the gas barrier sheet 1 </ b> A, and the moisture absorption formed by the material B that can maintain a solid state even when moisture is adsorbed. It can also have the form of gas barrier sheet 1G which provided film 13 further. Although details will be described later, this results in a moisture absorption film 13 in which moisture absorption is reversible, and as a result, the moisture absorption performance can be maximized by subjecting the gas barrier sheet 1G to a heating step before use. A gas barrier sheet 1G can be provided.

  As shown in FIG. 9, the gas barrier sheet 1 of the present invention may have a form of a gas barrier sheet 1 </ b> H in which a heat radiating gas barrier film 14 is further provided in the gas barrier sheet 1 </ b> G. More specifically, the gas barrier sheet 1 </ b> H includes a heat dissipating gas barrier film 14 between the gas barrier film 3 </ b> A and the moisture absorbing film 13. By using the gas barrier sheet 1H, when the object to be sealed with the gas barrier sheet 1H is exothermic, the heat dissipating gas barrier film 14 can be disposed at a position close to the object to be sealed. It becomes. Although details will be described later, it is possible to perform heat dissipation well even when the object to be sealed with the gas barrier sheet 1H is exothermic, and as a result, the gas barrier property is improved. It becomes easy to provide the gas barrier sheet 1H which not only becomes excellent but also has excellent heat dissipation.

  As shown in FIG. 10, the gas barrier sheet 1 of the present invention may have a form of a gas barrier sheet 1 </ b> I in which a heat radiating gas barrier film 14 is further provided in the gas barrier sheet 1 </ b> G. More specifically, in the gas barrier sheet 1I, the heat dissipating gas barrier film 14 is provided between the base material 2 and the anchor film 9A. As will be described in detail later, this makes it possible to perform heat dissipation well even when the object to be sealed with the gas barrier sheet 1I is exothermic. As a result, the gas barrier property is improved. It becomes easy to provide the gas barrier sheet 1I which is excellent in heat dissipation as well as being excellent.

  The layer structure of the gas barrier sheet of the present invention is not limited to the contents described above. For example, a gas barrier film may be formed instead of the hard coat film. In addition, the base material, the anchor film, the anchor film, and the gas barrier film are not necessarily in contact with each other. In some cases, between the base material and the anchor film (see, for example, the gas barrier sheet 1I in FIG. 10), the anchor film Another film may be appropriately inserted between the gas barrier film and the gas barrier film. Furthermore, the order of lamination of the respective films can be appropriately changed within the scope of the gist of the present invention. Such variations regarding the lamination of the films can be appropriately performed within the scope of the present invention.

(Base material)
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 Konica Katak 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 substrate 2 is usually 10 μm or more, preferably 50 μm or more, and usually 200 μm or less, preferably 150 μm or less, from the viewpoints of flexibility and shape retention.

  When the base material 2 is used as a substrate of a light emitting element such as an organic EL display that requires transparency, the base material 2 is preferably colorless and transparent. By making other films such as the gas barrier film 3 colorless and transparent together with the base material 2, the gas barrier sheet 1 can be made transparent. More specifically, for example, it is preferable that the substrate 2 has a transparency with an average light transmittance of 80% or more within a range of 400 nm to 700 nm. 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 is preferably smooth. 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 1 is applied to an organic EL display, it is required that the gas barrier sheet 1 is not 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 is subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, UV irradiation treatment, atmospheric pressure plasma treatment, and easy adhesion treatment. May be. As a specific method of such surface treatment, a conventionally known method can be appropriately used.

(Anchor membrane)
The anchor film 9 contains a polysiloxane polymer composed of a siloxane compound and a compound A having a functional group in the molecule that can react with a hydroxyl group of the siloxane compound during polymerization. More specifically, the polysiloxane polymer is obtained by polymerizing a siloxane compound and compound A. As a result, the structure of the polysiloxane polymer can be controlled to control the transparency, heat resistance, and rigidity of the anchor film 9, and as a result, it has excellent transparency, high heat resistance, and is difficult to curl. The gas barrier sheet 1 having excellent hard coat properties can be provided. More specifically, a polysiloxane polymer in which the degree of polymerization and the degree of crosslinking of the siloxane compound are controlled by the compound A can be obtained. For this reason, the transparency, heat resistance, and hardness of the anchor film 9 can be controlled by adjusting the ratio of Si—O bonds of the polysiloxane polymer. When the siloxane compound has a hydroxyl group, the siloxane compound and the compound A are polymerized by reacting the hydroxyl group with a functional group of the compound A. When the siloxane compound does not have a hydroxyl group, the siloxane compound is present in an alcohol solution or the like to exchange substituents and use the hydroxyl group formed in the siloxane compound. Thus, since the siloxane compound has a hydroxyl group at least at the time of polymerization, the hydroxyl group is allowed to react with the functional group of the compound A to advance the polymerization. That is, the “hydroxyl group possessed by the siloxane compound” may be considered to be a hydroxyl group originally possessed by the siloxane compound or a hydroxyl group formed on the siloxane compound during polymerization.

  In the anchor film 9, the Si—C bond in the anchor film 9 further improves the interaction with the base material 2. In particular, when a resin is used for the substrate 2, the affinity between the resin and the Si—C bond in the anchor film 9 is increased by providing the substrate 2 and the anchor film 9 in contact with each other. More specifically, when a polyester resin is used for the substrate 2, the interaction between the C—C bond of the polyester resin and the Si—C bond in the anchor film 9 is particularly high. As a result, the gas barrier sheet 1 excellent in adhesiveness can be provided.

  Examples of the siloxane compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane , Diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltribut Alkoxysilanes such as silane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and complex compounds thereof, methyltriacetoxy Examples thereof include silane, trimethylsilanol and the like, or high molecular organic compounds containing these compounds.

  Among the above siloxane compounds, from the viewpoint of controlling the reactivity during polymerization, it is preferable to use at least one of tetraethoxysilane, tetramethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, More preferably, at least one of tetraisopropoxysilane is used.

  The compound A having in the molecule a functional group capable of reacting with the hydroxyl group of the siloxane compound at the time of polymerization is used for controlling the degree of polymerization of the siloxane compound. By using the compound A, it is possible to control the stiffness of the anchor film 9 while ensuring the transparency of the anchor film 9, so that the curling of the anchor film 9 and thus the gas barrier sheet 1 is easily suppressed. Moreover, it becomes easy to ensure the hard coat property to the gas barrier sheet 1.

  Such a compound A is not particularly limited as long as it is a compound having in its molecule a functional group capable of reacting with a hydroxyl group in a siloxane compound during polymerization. Examples of such functional groups include epoxy groups, carboxyl groups, isocyanate groups, oxazolinyl groups, and groups derived from these functional groups.

  Examples of the compound A include methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl valerate, dimethyl oxalate, dimethyl malonate, dimethyl oxalate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, and valeric acid. Examples thereof include ethyl, diethyl oxalate, diethyl malonate, and diethyl oxalate. Among these compounds A, when using the method of forming the anchor film 9 using a coating liquid containing a polysiloxane polymer, from the viewpoint of suppressing poor coating properties of the coating liquid generated with the progress of the reaction, It is preferable to use at least one of methyl formate, methyl acetate, methyl propionate, dimethyl malonate, and dimethyl oxalate, and more preferably at least one of methyl formate, methyl acetate, dimethyl malonate, and dimethyl oxalate. .

  By controlling the polymerization ratio between the siloxane compound and compound A, the polysiloxane polymer can easily obtain desired transparency, heat resistance, and hardness. More specifically, the polysiloxane polymer is preferably composed of 70 mol% to 99 mol% of a siloxane compound and 1 mol% to 30 mol% of Compound A. As a result, the structure of the polysiloxane polymer can be controlled to adjust the transparency, heat resistance, and stiffness of the anchor film 9 more precisely. As a result, the transparency is excellent and the heat resistance is high. It is easy to provide a gas barrier sheet 1 that is high, difficult to curl, and excellent in hard coat properties. In particular, by controlling the hardness of the anchor film 9, it becomes easy to obtain the gas barrier sheet 1 that is not easily curled and has excellent hard coat properties.

  The polymerization ratio of the siloxane compound is usually 50 mol% or more, preferably 70 mol% or more as described above, and more preferably 75 mol% or more, more preferably 80 mol% from the viewpoint of improving the adhesion with the gas barrier film 3. That's it. On the other hand, the polymerization ratio of the siloxane compound is preferably 99 mol% or less as described above, but is preferably 95 mol% or less, more preferably 90 mol% or less, from the viewpoint of reducing the film stress.

  The polymerization ratio of Compound A is preferably 1 mol% or more as described above, but is preferably 5 mol% or more, more preferably 10 mol% or more from the viewpoint of increasing the reactivity. On the other hand, the polymerization ratio of the compound A is usually 50 mol% or less, preferably 30 mol% or less as described above, and when the method of forming the anchor film 9 using the coating liquid containing the polysiloxane polymer is used. From the viewpoint of maintaining the storage performance of the coating solution, it is more preferably 25 mol% or less, and even more preferably 20 mol% or less.

  The anchor film 9 may appropriately contain a material other than the polysiloxane polymer. For example, when using the method of forming the anchor film 9 using a coating solution containing a polysiloxane polymer, from the viewpoint of improving and ensuring the dispersibility of the coating solution, for example, sodium lauryl sulfate, polyvinyl alcohol, and A surfactant such as polyethylene glycol may be further contained. When a material other than the polysiloxane polymer is contained, the content is usually 3% by weight or more and 15% by weight or less.

  The extinction coefficient of the anchor film 9 is preferably 0.00001 or more and 0.01 or less. The extinction coefficient is more preferably 0.00005 or more, further preferably 0.0001 or more, more preferably 0.005 or less, and still more preferably 0.003 or less. By making the extinction coefficient in the above range, it becomes easy to ensure the transparency of the anchor film 9, and as a result, it becomes easy to obtain the gas barrier sheet 1 having high transparency.

  For the measurement of the extinction coefficient in the anchor film 9, a conventionally known method can be used, for example, an ellipsometer can be used. In the present invention, the extinction coefficient is measured by UVISEL ™ manufactured by JOBIN YVON. The measurement is 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 thickness of the anchor film 9 is usually 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.5 μm or more. If the thickness of the anchor film 9 is within the above range, the thickness of the anchor film 9 is sufficiently secured and the gas barrier sheet 1 is hardened, thereby making it easy to ensure hard coat properties. The thickness of the anchor film 9 is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less. When the thickness of the anchor film 9 is in the above range, it is easy to impart predetermined flexibility to the gas barrier sheet 1 while ensuring hard coat properties.

  The formation method of the anchor film 9 can be selected as appropriate. Examples of such a method include a method obtained by applying a coating liquid containing a polysiloxane polymer or the like on the substrate 2 and then drying it.

  The coating solution for the polysiloxane polymer is usually prepared by adjusting an appropriate solvent, and adding the siloxane compound and compound A in the solvent at a predetermined ratio to polymerize the polysiloxane polymer, and if necessary, polysiloxane. It can be obtained by adding a material other than a polymer. One type of solvent may be sufficient and two or more types of mixed solvents may be sufficient. When a mixed solvent is used, for example, methanol, ethanol, isopropanol, t-butanol, or the like can be used as the main solvent. From the viewpoint of increasing the uniformity of the coated surface, as a secondary solvent, for example, a low boiling point solvent such as formic acid, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, cyclohexanone, diethylene glycol One or more high-boiling solvents such as dimethyl ether, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide can be used. The content of the main solvent in the mixed solvent is usually 60% by weight or more and 90% by weight or less. However, the composition of the solvent is adjusted depending on the surface shape and hydrophilicity / hydrophobicity of the substrate 2. For example, for a water-repellent substrate 2 having a high contact angle, an ether having a large number of hydrophobic groups and a saturated hydrocarbon may be used as the main solvent.

  When the siloxane compound and the compound A are polymerized, the ratio of the siloxane compound and the compound A, the charging method, the temperature, the atmosphere, and the like may be appropriately controlled. Specifically, the input ratio may be appropriately controlled in the siloxane compound and compound A in consideration of the desired polymerization ratio described above. In order to smoothly polymerize the polysiloxane polymer, it is preferable that the siloxane compound and compound A are not added all at once, but the input amount is controlled and gradually added. Furthermore, the temperature may be usually -20 ° C or higher and 60 ° C or lower. The atmosphere during the polymerization is preferably performed in an inert atmosphere in order to prevent oxidation and the like. Examples of the inert atmosphere include an argon atmosphere and a nitrogen atmosphere. In addition, conventionally known control may be appropriately performed in order to obtain a desired polysiloxane polymer.

  Further, after polymerizing the polysiloxane polymer, from the viewpoint of controlling the thickness of the anchor film 9, an additional solvent may be added to adjust the solid content concentration. At least a part of the solvent at this time is preferably a solvent similar to that used during polymerization. For example, when a mixed solvent is used, it is preferable to use at least a solvent similar to the main solvent.

  The polysiloxane polymer coating solution thus obtained is applied onto the substrate 2 using, for example, a screen printing method, a roll coating method, a Miya bar coating method, a gravure coating method, a spin coating method, a die coating method, or the like. The anchor film 9 can be obtained by drying. Among the above coating methods, it is preferable to use a die coating method in view of industrial productivity and ease of thickness control. In drying, the drying temperature and time may be appropriately controlled in consideration of the boiling point of the solvent used.

  Whether or not the obtained anchor film 9 contains a desired polysiloxane polymer can be analyzed using a conventionally known analysis method. An example of such an analysis method is an XPS (X-ray photoelectron analyzer) method. In the present invention, XPS is measured by XPS (ESCA LAB220i-XL apparatus 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 is used, and a slit having a diameter of about 1 mm is used. The measurement is performed with the detector set on the normal line of the sample surface subjected to the measurement, and appropriate charge correction is performed. The analysis after the measurement is performed using software Eclipse version 2.1 attached to the above-described XPS apparatus, and using peaks corresponding to the binding energy of Si: 2p, C: 1s. At this time, among the peaks of C: 1s, each peak shift is corrected with the peak corresponding to the hydrocarbon as a reference, and the binding state of the peaks is attributed. In addition to the hydrocarbon peak position, the peak of carbonyl bond, etc. is compound A, the Si peak is a siloxane compound, Shirley background is removed for each peak, and the sensitivity coefficient of each element in the peak area Correction (Si = 0.87 with respect to C = 1.0) is performed to determine the atomic ratio. Moreover, the polymerization ratio of the siloxane compound to the compound A in the polysiloxane polymer can be estimated from the atomic ratio of Si and the atomic ratio of carbonyl bonds or the like in the composition analysis using the above measurement method.

(Gas barrier film)
In the gas barrier film 3, a SiN _x O _y film (where x = 0.5 to 1.5, y = 0.15 to 1) is used.

  By using the gas barrier film 3 described above, the amount of Si—N bonds per unit thickness can be increased, and the density of the gas barrier film 3 can be increased to easily improve the gas barrier property of the gas barrier film 3. Curling is less likely to occur by reducing the film stress by introducing a certain amount of oxygen. In particular, even after a heat cycle test performed as a durability test for an organic EL display or the like, it is possible to provide the gas barrier sheet 1 in which the occurrence of curling is suppressed and the gas barrier performance is maintained.

  Further, in the gas barrier sheet 1, the gas barrier property can be ensured by two layers of the anchor film 9 and the gas barrier film 3. As a result, it is possible to provide a gas barrier sheet 1 that is particularly excellent in gas barrier properties. Further, when the gas barrier film 3 and the anchor film 9 are provided in contact with each other, Si is present in both the gas barrier film 3 and the anchor film 9 by making the gas barrier film 3 the silicon oxynitride film. The interaction between the gas barrier film 3 and the anchor film 9 is enhanced. As a result, the gas barrier sheet 1 excellent in adhesiveness can be provided.

As the gas barrier film 3, an SiN _x O _y film (where x = 0.5 to 1.5, y = 0.15 to 1) is used. The SiN _a O _b film conventionally used for the purpose of gas barrier was a = 0.5, b = 1.5 or a = 1.4, b = 0.1. By using the predetermined SiN _x O _y film, it is possible to secure an appropriate amount of oxygen for imparting flexibility to the gas barrier film 3 while ensuring the amount of Si—N bonds that contribute to gas barrier properties. As a result, the gas barrier property is increased and curling is easily suppressed.

_{X in} the SiN _x O _y film of the gas barrier film 3 is 0.5 or more, preferably 0.7 or more, and 1.5 or less, preferably 1.3 or less. If it is the said range, it will become easy to improve the gas barrier property of the gas barrier film 3 by ensuring the quantity of Si-N bond in the gas barrier film 3. On the other hand, y is 0.15 or more, preferably 0.25 or more, more preferably 0.3 or more, and 1 or less, preferably 0.7 or less. If it is the said range, content of oxygen in the gas barrier film 3 will be ensured, and it will become easy to provide a softness | flexibility to the gas barrier film 3. Note that the gas barrier film 3 may contain elements and substances other than Si, N, and O as impurities and additives as long as they are within the scope of the present invention.

Whether or not the gas barrier film 3 is a predetermined SiN _x O _y film can be confirmed by, for example, determining the atomic ratio of Si, N, and O. As a method for obtaining such an atomic ratio, a conventionally known method can be used, and for example, evaluation can be made based on results obtained by an analyzer such as XPS (X-ray photoelectron analyzer). In the present invention, XPS is 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 is used, and a slit having a diameter of about 1 mm is used. The measurement is performed with the detector set on the normal line of the sample surface subjected to the measurement, and appropriate charge correction is performed. The analysis after the measurement uses the software Eclipse version 2.1 attached to the above-mentioned XPS apparatus, and uses peaks corresponding to the binding energies of Si: 2p, C: 1s, N: 1s, and O: 1s. Is going. At this time, among the peaks of C: 1s, each peak shift is corrected with the peak corresponding to the hydrocarbon as a reference, and the binding state of the peaks is attributed. Then, background of Shirley is removed for each peak, and sensitivity coefficient correction of each element is performed on the peak area (Si = 0.87, N = 1.77, O = 2 with respect to C = 1.0). .85) to obtain the atomic ratio. With respect to the obtained atomic ratio, the number of Si atoms is set to 1, and the number of atoms of N and O, which are other components, is calculated and used as the component ratio.

  The thickness of the gas barrier film 3 is usually 10 nm or more, preferably 30 nm or more, and usually 200 nm or less, preferably 150 nm or less. When the thickness of the gas barrier film 3 is in the above range, the gas barrier property of the gas barrier film 3 is enhanced and the occurrence of curling is easily suppressed.

  When the gas barrier film 3 is used as a gas barrier film of a light-emitting element such as an organic EL display that requires transparency, the gas barrier film 3 is preferably transparent. By making other films such as the substrate 2 transparent together with the gas barrier film 3, the gas barrier sheet 1 can be made transparent. More specifically, for example, it is preferable that the gas barrier film 3 has a transparency with an average light transmittance of 75% or more in a range of 400 nm to 700 nm. Since such light transmittance is influenced by the composition and thickness of the gas barrier film 3, it is configured taking both into consideration.

  In order to ensure the transparency of the gas barrier film 3, the extinction coefficient of the gas barrier film 3 is preferably set to 0.000001 or more and 0.01 or less. The extinction coefficient is more preferably 0.000005 or more, further preferably 0.00001 or more, and more preferably 0.005 or less. By setting the extinction coefficient in the above range, it becomes easy to ensure the transparency of the gas barrier film 3, and as a result, it becomes easy to obtain the highly transparent gas barrier sheet 1.

  The measurement of the extinction coefficient in the gas barrier film 3 can use a conventionally known method, for example, an ellipsometer. In the present invention, the extinction coefficient is measured by UVISEL ™ manufactured by JOBIN YVON. The measurement is 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 gas barrier film 3 is formed by agglomeration of secondary particles, and the particle size of the secondary particles is preferably 300 nm or more and 1500 nm or less. As a result, the adjacent secondary particles are sufficiently aggregated. As a result, the gas barrier property can be ensured while maintaining the flexibility of the base material without reducing the productivity. Although details of the measuring method will be described later, the particle size of the secondary particles is obtained by observing the surface of the gas barrier film 3 and measuring the particle size of the secondary particles observed on the surface.

  The gas barrier film 3 is usually formed by agglomeration of secondary particles. Here, from the viewpoint of ultimately improving the gas barrier property, it is ideal that the boundary between particles is not observed and the gas barrier film 3 is continuously formed. However, it is not easy to create such a state. For example, even when the gas barrier film 3 formed (film formation) on the base material 2 is fired at high temperature using the base material 2 (for example, glass) capable of high-temperature firing, the particle interface between the secondary particles Is difficult to remove completely, and a hard thin film is formed, lacks flexibility, and easily cracks. However, the gas barrier film 3 obtained by firing at a high temperature has improved gas barrier properties as compared to before firing as a result of the progress of simultaneous aggregation of adjacent secondary particles. On the other hand, as the base material 2, it is required to use various materials such as a resin as described above, and a material that does not have heat resistance enough to withstand high-temperature firing may be used. For this reason, it is difficult to industrially fire the gas barrier film 3 after film formation at a high temperature. Moreover, it is difficult to perform such a baking process newly from the viewpoint of ensuring production efficiency. Furthermore, if the flexibility of the gas barrier film 3 is impaired by high-temperature firing, it is difficult to obtain the flexibility that is a characteristic exhibited when the resin base material 2 is used. Therefore, it is desired that the gas barrier film 3 having the gas barrier property as high as the gas barrier film 3 baked at a high temperature without losing flexibility is desired in a state where the gas barrier film 3 is formed.

  As a result of the inventor's repeated studies on the state of the gas barrier film 3, when the gas barrier film is formed (deposition) using an ion plating method described later, the plasma acts as a substitute for heat and the film is formed. It was found that the gas barrier property can be easily ensured immediately after the reaction similar to the high temperature firing can be obtained. Therefore, the flexible gas barrier film 3 which is not a hard thin film is obtained, and it becomes easy to obtain the gas barrier sheet 1 having excellent gas barrier properties while ensuring the flexibility of the substrate 2. Specifically, by using the ion plating method, aggregation of secondary particles occurs, the particle size of the secondary particles tends to be 300 nm or more and 1500 nm or less, and the gas barrier property is more easily secured without impairing flexibility. I understood it. From the viewpoint of further ensuring gas barrier properties, the particle size of the secondary particles is more preferably 330 nm or more, further preferably 400 nm or more, and more preferably 1000 nm or less.

  The secondary particle diameter of the gas barrier film 3 can be controlled by using the ion plating method as described above, but can also be controlled by the state of the anchor film 9. Specifically, by providing the gas barrier film 3 in contact with the anchor film 9, the secondary particle diameter can be easily controlled within the above particle diameter range.

  In the gas barrier film 3, the distance between adjacent secondary particles is preferably 100 nm or more and 300 nm or less. Thereby, since aggregation of adjacent secondary particles is promoted, as a result, it is possible to provide the gas barrier sheet 1 that can easily maintain the flexibility of the base material. The distance between adjacent secondary particles can be determined by measuring the distance between the end portions of the particles obtained by circular approximation of the adjacent secondary particles. Although the details of the measurement method will be described later, the distance between the secondary particles is obtained by observing the surface of the gas barrier film 3 and measuring the distance between the ends of adjacent secondary particles observed on the surface. It is.

  For the measurement of the secondary particle diameter constituting the gas barrier film 3 and the distance between adjacent particles, a conventionally known method may be used as appropriate. For example, measurement is performed using an atomic force microscope (AFM). be able to. Specifically, Nanopics-1000 manufactured by Seiko Instruments Inc. may be used, and the measurement may be performed under the measurement conditions in which the observation mode is the contact mode, the scan range is 4 μm square, and the scan speed is 90 seconds / frame. Subsequently, arbitrary 30 points are set by trackball operation on analysis software installed in a personal computer or the like. And the least square method circle approximation is performed with respect to the point, and let the average value be a secondary particle diameter. The distance between adjacent particles is obtained by calculating an average value between the end portions of the particles calculated by the above-described circle approximation. Instead of the trackball, other input devices such as a mouse and a keyboard may be used as appropriate.

  The method for producing the gas barrier film 3 is not particularly limited, and for example, a vacuum deposition method, a sputtering method, an ion plating method, a Cat-CVD method, a plasma CVD method, an atmospheric pressure plasma CVD method, or the like may be used. 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.

  The vacuum vapor deposition method is a method of obtaining a gas barrier film 3 by heating and evaporating the material contained in the crucible by resistance heating, high frequency induction heating, beam heating such as an electron beam or ion beam, etc. is there. At this time, the heating temperature and the heating method can be changed depending on the composition of the gas barrier film 3, and a reactive vapor deposition method that causes an oxidation reaction or the like during film formation can also be used.

  Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is made to collide with the target, atoms on the target surface are ejected, and attached to the anchor film 9, This is a method for obtaining the gas barrier film 3. At this time, a reactive sputtering method may be used in which a gas barrier film 3 is formed by reacting an element ejected from the target with nitrogen or oxygen by flowing nitrogen gas or oxygen gas into the chamber. 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. In the ion plating method, reactive ion plating in which a reactive gas plasma is combined with evaporated particles to synthesize a compound film is effective. Since the operation is in plasma, the first condition is to obtain a stable plasma. In many cases, low-temperature plasma using weakly ionized plasma in a low gas pressure region is used. For this reason, it is preferably used when a mixture or a complex oxide is formed. The means for generating a discharge is roughly classified into a direct current excitation type and a high frequency excitation type. In addition, a hollow cathode or an ion beam may be used for the evaporation mechanism.

  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).

The gas barrier film 3 is a SiN _x O _y film (x = 0.5 to 1.5, y = 0.15 to 1), and the control of the composition of the SiN _x O _y film has been introduced above. It can be performed by appropriately changing the manufacturing conditions while appropriately using the manufacturing method.

(Transparent conductive film)
The transparent conductive film 4 is provided on the gas barrier film 3. More specifically, as shown in FIG. 2, in the gas barrier sheet 1B, the transparent conductive film 4 is provided on the gas barrier film 3A. Since the transparent conductive film 4 can be used as an anode of an organic EL display, or can impart a heat dissipation function and an antistatic function to the gas barrier sheet 1B, the productivity of the organic EL display can be provided by providing the transparent conductive film 4. And can improve the service life.

When the anode is already provided in the organic EL display, the transparent conductive film 4 may be provided for the purpose of imparting antistatic performance and heat dissipation function to the gas barrier sheet 1B. Specifically, when the organic EL display is encapsulated (sealed) with the gas barrier sheet 1B, the transparent conductive film 4 releases the Joule heat generated in the organic EL display and releases the external charges charged on the film. Such a function can be given. For example, the transparent conductive film 4 can be provided in order to suppress element deterioration due to heat generation, which is a problem of the organic EL display. However, when providing the antistatic function and the heat dissipation function using the transparent conductive film 4, the transparent conductive film 4 may be in contact with the electrode of the organic EL display. In this case, it is preferable to appropriately control the conductivity so that current does not leak from the electrode. Specifically, the surface resistance value of the transparent conductive film 4 is preferably controlled to 10 ⁴ Ω / □ or more and 10 ⁶ Ω / □ or less. On the other hand, when the transparent conductive film 4 and the electrode of the organic EL display are insulated by interposing an adhesive layer or the like therebetween, the degree of freedom in controlling the conductivity is increased. Specifically, in this case, the surface resistance value of the transparent conductive film 4 can be controlled to 10 ⁴ Ω / □ or more and 10 ¹² Ω / □ or less. Further, from the viewpoint of ensuring thermal conductivity, the thermal conductivity of the transparent conductive film 4 is usually 0.5 W / mK or more, preferably 1 W / mK or more, and usually 10 W / mK or less, preferably 8 W / mK or less. Be controlled.

  The surface resistance value of the transparent conductive film 4 can be measured by a conventionally known method. In the present invention, the surface resistance value is measured by Hiresta UP (MCP-HT450) which is a high resistivity meter manufactured by Dia Instruments Co., Ltd. It is measured using. Further, the thermal conductivity of the transparent conductive film 4 can also be measured by a conventionally known method. In the present invention, the measurement is performed using a steady-state thermal conductivity measuring device GH series manufactured by ULVAC-RIKO. .

  It is preferable to impart conductivity to the transparent conductive film 4. From such a viewpoint, the transparent conductive film 4 may be a coating film mainly composed of an inorganic oxide formed by applying a hydrolyzate such as a metal alkoxide, or a hydrolyzate such as a transparent conductive particle and a metal alkoxide.

In addition, the transparent conductive film 4 is formed by vacuum deposition such as resistance heating vapor deposition, induction heating vapor deposition, EB vapor deposition, sputtering, ion plating, thermal CVD, and plasma CVD from the viewpoint of imparting conductivity. It may be a film formed by a film method. The transparent conductive film 4 can be formed using an EB vapor deposition method, a sputtering method, or an ion plating method because the resistance value can be lowered and an apparatus configuration capable of surface treatment is possible. The material of the transparent conductive film 4 in the case of using such a forming method is, for example, indium-tin-based oxide (ITO), indium-tin-zinc-based oxide (ITZO), zinc oxide-based such as ZnO ₂ , CdO-based, And SnO ₂ (tin oxide) -based, indium oxide, indium-zinc-based oxide (IZO), aluminum-added zinc oxide, gallium-added zinc oxide, antimony-added tin oxide, etc .; gold, silver, copper, aluminum, palladium Examples of such a metal include oxide and metal laminates. Such a material may be appropriately selected and used, but among the above materials, indium-tin oxide (ITO) is preferable in terms of excellent transparency and conductivity. Further, in the case of imparting a heat dissipation function to the transparent conductive film 4, it is preferable to use a material that absorbs infrared light as the transparent conductive film 4 from the viewpoint of enhancing the heat dissipation effect. It is preferable to use an object (ITO). When indium-tin oxide (ITO) is used, it is particularly preferable to use one having a tin content of 5 to 15 mol%.

  The thickness of the transparent conductive film 4 is usually 10 nm or more, preferably 60 nm or more, more preferably 100 nm or more. If it is the said range, it will become easy to ensure the electroconductivity and heat dissipation of the transparent conductive film 4. FIG. The thickness of the transparent conductive film 4 is usually 1000 nm or less, preferably 450 nm or less, more preferably 200 nm or less. If it is the said range, it will be easy to ensure the transparency of the transparent conductive film 4, and it will become easy to also bend resistance.

(Hard coat film)
As shown in FIG. 3, the hard coat film 5 is provided on at least one side of the gas barrier sheet 1C. More specifically, the hard coat film 5 is provided on the other surface 12 of the substrate 2, that is, the surface opposite to the surface on which the anchor film 9 </ b> A is formed on both surfaces of the substrate 2. Thereby, since the gas barrier sheet 1C is protected by the hard coat film 5, as a result, it becomes easier to provide the gas barrier sheet 1C which is hardly damaged.

  As the hard coat film 5, a conventionally known film can be appropriately used. Specifically, as the material of the hard coat film 5, those having an acrylate functional group which is an ionizing radiation curable resin, that is, those having an acrylic skeleton and those having an epoxy skeleton are suitable. Considering the hardness, heat resistance, solvent resistance, and scratch resistance of the film 5, it is preferable to have a high crosslink density structure. As materials for obtaining such a structure, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Bifunctional or higher acrylate monomers such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate can be exemplified. In the above, “(meth) acrylate” means both acrylate and methacrylate.

  When the ionizing radiation curable resin is used as the material for the hard coat film 5, a known photopolymerization initiator or photosensitizer can be used in combination. Such photopolymerization initiators and photosensitizers are preferably used when the ionizing radiation curable resin is cured by irradiating ultraviolet rays. This is because ionizing radiation curable resins tend to be sufficiently cured when irradiated with an electron beam. The addition amount of the photopolymerization initiator or photosensitizer is generally 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the ionizing radiation curable resin. In addition to these materials, various inorganic and organic additives such as a solvent, a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener can be added as necessary.

The hard coat film 5 can be formed by applying the above material as a coating solution on the substrate 2 and curing it. Here, the coating amount of the coating solution is usually 0.5 g / m ² or more and 15 g / m ² or less as the solid content. In addition, as an ultraviolet-ray source used for hardening, an ultrahigh pressure mercury lamp etc. can be mentioned, for example. As a wavelength of ultraviolet rays, a wavelength range of 190 nm or more and 380 nm or less can be used normally, and as an electron beam source, various electron beam accelerators such as a cockcroft-walt type can be used.

  The thickness of the hard coat film 5 is usually 1 μm or more, preferably 3 μm or more, and usually 10 μm or less, preferably 8 μm or less. If it is in this range, the transparency of the gas barrier sheet 1C is hardly impaired, and the scratch resistance tends to be good.

(Hygroscopic film)
The hygroscopic film 13 is provided on at least one side of the gas barrier sheets 1G, 1H, and 1I as shown in FIGS. The moisture absorption film 13 is formed of a material B that can absorb and desorb moisture and can maintain a solid state even when moisture is adsorbed. As a result, the moisture absorption film 13 is reversible in moisture absorption. As a result, the gas barrier property can be maximized by subjecting the gas barrier sheets 1G, 1H, 1I to a heating step before use. Sheets 1G, 1H, and 1I can be provided.

  More specifically, when the gas barrier sheet 1 is used as a sealing film for an organic EL display, the organic EL display, which is an object to be sealed, forms a dark spot by adsorbing moisture, so that moisture is surely secured. It is desirable to use a gas barrier sheet 1 having a high gas barrier property that can be blocked. In this case, the anchor film 9 and the gas barrier film 3 may be difficult to reliably block water vapor. Therefore, by using the gas barrier sheet 1G, 1H, 1I provided with the moisture absorption film 13 on the surface to seal the object to be sealed, the moisture barrier property (water vapor barrier property) can be further increased. It becomes easier to improve the durability of the organic EL display. Further, by using the material B for the hygroscopic film 13, it becomes possible to adsorb moisture or form hydrated water by a reversible reaction, and perform heating or infrared irradiation before sealing the organic EL display element. As a result, the moisture adsorbed on the moisture absorption film 13 can be almost removed, so that it becomes possible to manufacture an organic EL display with the maximum moisture absorption performance.

  As the material B, as described above, a material that can adsorb and desorb moisture and can maintain a solid state even when moisture is adsorbed may be used. Here, the adsorption of moisture includes, for example, a case where water is physically adsorbed and a case where it is chemically adsorbed. And as a case where moisture chemically adsorbs, a case where moisture forms a hydrate with the material B, a case where moisture becomes a hydroxide and chemically bonds to the material B, and the like can be mentioned. However, even though the material B can adsorb and desorb moisture, in the present invention, a material having a property of easily adsorbing moisture but not easily desorbing is used as the material B. This is because the moisture-absorbing film 13 tends not to exhibit the performance as a film having hygroscopicity with a material that easily desorbs moisture. That is, although the moisture absorption of the moisture absorption film 13 is reversible, the moisture absorption film 13 is basically moisture absorption, and the desorption of moisture is not performed until the moisture absorption film 13 is processed at a high temperature. Become. For example, in the case where a material that chemically bonds with moisture as a hydroxide is used for the material B, the moisture once adsorbed as a hydroxide is not desorbed unless it is treated at a high temperature (for example, about 600 ° C.). .

  The material B is not particularly limited, but is preferably an alkali metal oxide or an alkaline earth metal oxide from the viewpoint described above. Accordingly, the material B having good moisture absorption characteristics is used for the moisture absorption film 13, and as a result, the gas barrier sheets 1G, 1H, and 1I having the moisture absorption film 13 having high moisture absorption characteristics can be provided. For example, when a metal is used as the material B, when the object to be sealed is an organic EL display, the opening is narrowed and high resolution may not be obtained.

  The alkali metal oxide is not particularly limited, but sodium oxide (sodium oxide) and potassium oxide (potassium oxide) are preferably used from the viewpoints of stability, hygroscopic performance and the like. Further, the alkaline earth metal oxide is not particularly limited, but from the viewpoint of stability, moisture absorption performance, etc., calcium oxide (calcium oxide), strontium oxide (strontium oxide), barium oxide (barium oxide) Is preferably used.

  In the moisture absorption film | membrane 13, you may contain materials other than the material B according to the desired characteristic.

The extinction coefficient of the hygroscopic film 13 is preferably 1 × 10 ⁻⁶ or more and 1 × 10 ⁻³ or less. The extinction coefficient is more preferably 1 × 10 ⁻⁵ or more, further preferably 2 × 10 ⁻⁵ or more, particularly preferably 3 × 10 ⁻⁵ or more, more preferably 5 × 10 ⁻⁴ or less, still more preferably. 1 × 10 ⁻⁴ or less. By making the extinction coefficient in the above range, it becomes easy to ensure the transparency of the moisture absorption film 13, and as a result, it becomes easy to obtain the gas barrier sheets 1G, 1H, 1I having excellent transparency.

  For the measurement of the extinction coefficient in the hygroscopic film 13, the same measurement method as that for the anchor film 9 and the gas barrier film 3 can be used.

  The thickness of the hygroscopic film 13 is usually 10 nm or more, preferably 30 nm or more, more preferably 50 nm or more. If the thickness of the hygroscopic film 13 is within the above range, the thickness of the hygroscopic film 13 can be sufficiently secured to easily absorb moisture, and the gas barrier property can be easily improved. The thickness of the hygroscopic film 13 is usually 1000 nm or less, preferably 500 nm or less, and more preferably 300 nm or less. When the thickness of the hygroscopic film 13 is in the above range, it becomes easy to impart predetermined transparency and flexibility to the gas barrier sheets 1G, 1H, and 1I while ensuring the moisture absorption.

  The formation method of the moisture absorption film | membrane 13 can be selected suitably. As such a method, for example, when an alkali metal oxide or an alkaline earth metal oxide is used as the material B, the moisture absorption film 13 may be formed by vacuum film formation. As a method of vacuum film formation, the same method as described for the gas barrier film 3 (for example, vacuum deposition method, sputtering method, ion plating method, Cat-CVD method, plasma CVD method, atmospheric pressure plasma CVD method) is used. It can be used as appropriate.

(Heat-dissipating gas barrier film)
In the gas barrier sheets 1H and 1I, a heat radiating gas barrier film 14 is further provided as shown in FIGS. As a result, even when the object to be sealed with the gas barrier sheets 1H and 1I is exothermic, the heat dissipation can be performed well, and as a result, the gas barrier property is excellent. It becomes easy to provide not only the gas barrier sheet | seat 1H and 1I which is excellent also in heat dissipation. In particular, in the gas barrier sheet 1H, when the object to be sealed is exothermic, the heat dissipating gas barrier film 14 can be disposed at a position close to the object to be sealed.

  The material used for the heat dissipating gas barrier film 14 may be any material having desired gas barrier properties and heat dissipating properties, but it is preferable to use a metal compound or diamond-like carbon from the viewpoint that heat dissipating properties are easily secured. Examples of the metal compound include aluminum nitride, titanium nitride, zinc oxide, alumina, boron nitride, and the like, preferably aluminum nitride and titanium nitride. From the viewpoint of facilitating ensuring the transparency of the heat dissipating gas barrier film 14, it is preferable to use diamond-like carbon.

  Diamond-like carbon (DLC) used as a material for the heat-dissipating gas barrier film 14 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 sheets 1H and 1I are used as a display substrate or a sealing film for a display such as an organic EL display, a short circuit between the cathode and the anode of the display can be achieved. It becomes easy to suppress.

  The thermal conductivity of the heat dissipating gas barrier film 14 is usually 20 W / mK or more, preferably 30 W / mK or more. By setting the thermal conductivity within the above range, the heat dissipation of the gas barrier sheets 1H and 1I can be more easily ensured. The higher the thermal conductivity, the better because it is excellent in heat dissipation, but it is usually 2000 W / mK or less.

  The thermal conductivity of the heat dissipating gas barrier film 14 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.). can do.

  The thickness of the heat dissipating gas barrier film 14 is usually 2 nm or more, preferably 5 nm or more, and usually 70 nm or less, preferably 60 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 method for forming the heat-dissipating gas barrier film 14 can be selected as appropriate. Examples of such a method include a sputtering method, an ion plating method, a CVD (Chemical Vapor Deposition) method, and a plasma CVD method. 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.

(Other membranes)
In addition to the base material 2, the anchor film 9, the gas barrier film 3, the transparent conductive film 4, the hard coat film 5, the hygroscopic film 13, and the heat dissipating gas barrier film 14 described above, other films may be used as necessary. You can also. Examples of such a film include an antireflection film, an antistatic film, an antifouling film, an antiglare film, a color filter, and a smoothing film. Among these, an antireflection film, an antistatic film, an antifouling film, an antiglare film, and a color filter may obtain a desired function by being bonded to the gas barrier sheet of the present invention via an optical adhesive. .

  The anti-reflective film has a function to suppress the reflection of external light, the anti-static film has a function to prevent dust and dirt from adhering, and the anti-fouling film inhibits adhesion of oil such as fingerprints. Conventionally known ones may be used as appropriate, but they are often formed on the surface of the hard coat film 5. However, an antireflection function or a transparent conductive function can be added to the hard coat film 5. The smoothing film is used to flatten the surface, and may be formed on the surface of the base material 2 or the surface of the gas barrier film 3, for example. The antireflection film is not particularly limited as long as it has a function of suppressing reflection of external light, but an optical multilayer film by optical interference, an antiglare film using a light scattering effect by fine particles, a microlens array, A moth-eye structure is mentioned.

  As the smoothing film, a conventionally known film may be appropriately used. Examples of the material for the smoothing film include sol-gel materials, ionizing radiation curable resins, thermosetting resins, and photoresist materials.

  In the case of forming the smoothing film on the surface of the gas barrier film 3, it is preferable to use an ionizing radiation curable resin as the material of the smoothing film from the viewpoint of facilitating the formation of the film while maintaining the gas barrier function. More specifically, an ionizing radiation curable resin that is an appropriate mixture of reactive prepolymers, oligomers, and / or monomers having an epoxy group, or a urethane-based ionizing radiation curable resin as necessary. It has a polymerizable unsaturated bond in the molecule, such as a liquid composition obtained by mixing a thermoplastic resin such as polyester, acrylic, butyral, or vinyl, and has ultraviolet (UV) or electron A resin that undergoes a crosslinking polymerization reaction and changes to a three-dimensional polymer structure by irradiating the line (EB) is preferable. The smoothing film can be formed by applying, drying, and curing such a resin by a conventionally known coating method such as a roll coating method, a Miya bar coating method, and a gravure coating method. The smoothing film may be formed by the same method as the hard coat film 5.

  In the case where the smoothing film is formed on the surface of the gas barrier film 3, a coating film of the same material system as the gas barrier film 3 is used as the material of the smoothing film from the viewpoint of ensuring good adhesion to the gas barrier film 3. It is also preferable to use a sol-gel material using a sol-gel method that can be formed. The sol-gel method includes at least a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent. It refers to the coating method of the paint composition and the coating film. As the silane coupling agent having an organic functional group and a hydrolyzable group, conventionally known silane coupling agents can be appropriately used. For example, aminoalkyl dialkoxysilanes and aminoalkyltrialkoxy disclosed in JP-A-2001-207130. Silane may be used. Examples of the crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent include functional groups capable of reacting with amino groups such as glycidyl group, carboxyl group, isocyanate group, and oxazoline group. The thing which has can be mentioned. Conventionally known materials can be used as appropriate. Furthermore, various inorganic and organic additives such as a solvent, a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a thickener are added to the coating composition as necessary. Can do.

  Furthermore, as a material for the smoothing film, a conventionally known cardo polymer is preferably contained.

  The thickness of the smoothing film is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 10 μm or less, preferably 5 μm or less.

(Gas barrier sheet)
By having the base material 2, the anchor film 9, the gas barrier film 3, the transparent conductive film 4, the hard coat film 5, the hygroscopic film 13, the heat dissipating gas barrier film 14, and other films as necessary, the gas barrier is provided. The sheet 1 is formed. The gas barrier sheet 1 contains the predetermined polysiloxane polymer in the anchor film 9, and the gas barrier film 3 has a predetermined composition, thereby controlling the structure of the polysiloxane polymer and the transparency of the anchor film 9. Heat resistance and hardness can be controlled, and the gas barrier property can be secured with two layers of the anchor film 9 and the gas barrier film 3, and the base material 2, the anchor film 9 and the gas barrier film 3 are provided in contact with each other. In this case, the interaction between the anchor film 9 and the gas barrier film 3 is enhanced by the Si in the anchor film 9 and the Si in the gas barrier film 3, and the Si—C bond in the anchor film 9 is bonded to the base material 2. To improve the interaction. As a result, it is possible to provide the gas barrier sheet 1 having excellent transparency, high heat resistance, hardly curling, excellent hard coat properties, excellent gas barrier properties, and excellent adhesion.

The gas barrier sheet 1 usually has a water vapor transmission rate of 0.1 g / m ² / day (g / m ² · day) or less and an oxygen transmission rate of 0.1 cc / m ² / day · atm (cc / m ^2). (Day.atm) High gas barrier property is shown.

  When the gas barrier sheet 1 is used as a gas barrier sheet of a light emitting device such as an organic EL display that requires transparency, the gas barrier sheet 1 is preferably transparent. In this case, specifically, the total light transmittance is preferably 75% or more, more preferably 80% or more. Further, the color (YI) is preferably 5 or less, more preferably 3 or less. Since the gas barrier sheet 1 appears yellow as YI increases, it is preferable to control YI within the above range in appearance. The total light transmittance and YI can be measured using, for example, a spectrocolorimeter. In the present invention, total light transmittance and YI are measured using SM color computer SM-C (manufactured by Suga Test Instruments). And the measurement is implemented based on JISK7105.

  In the gas barrier sheet 1, the occurrence of curling is suppressed by the combination of the predetermined anchor film 9 and the predetermined gas barrier film 3. FIG. 5 is a schematic cross-sectional view showing a method for measuring the degree of curling of the gas barrier sheet. First, the gas barrier sheet 1 is cut out to a predetermined size to prepare a gas barrier sheet sample 10. Then, the gas barrier sheet sample 10 is placed on the stainless steel substrate 6, and the orthogonal distance L between the vertex 8 of the gas barrier sheet sample 10 and the stainless steel substrate 6 is measured. And according to the magnitude | size of the orthogonal distance L, what is necessary is just to evaluate the generation | occurrence | production degree of the curl of a gas barrier sheet using a predetermined evaluation standard.

  Further, a heat resistance test (heat cycle test) is performed on the gas barrier sheet sample 10, and the orthogonal distance L is measured again after the heat cycle test to evaluate the curl degree of the gas barrier sheet 1 after the heat cycle test. It can also be done. Specifically, the heat cycle test is performed by repeatedly performing the operation of holding the gas barrier sheet sample 10 in an oven at 150 ° C. for 3 hours 5 times. Then, the gas barrier sheet sample 10 after the heat cycle test is placed on the stainless steel substrate 6 again, and the orthogonal distance L between the apex of the gas barrier sheet sample 10 and the stainless steel substrate 6 is measured. And according to the magnitude | size of the orthogonal distance L, what is necessary is just to evaluate the generation | occurrence | production degree of the curl of the gas barrier sheet 1 using a predetermined evaluation standard. The orthogonal distance L evaluated by such a method is usually controlled to be 3 mm or less before and after the heat cycle test. From the viewpoint of obtaining a higher performance gas barrier sheet 1, it is preferable to control the orthogonal distance L to be 1 mm or less.

  When the base material 2, the anchor film 9, and the gas barrier film 3 are provided in contact with each other by a combination of the predetermined anchor film 9 and the predetermined gas barrier film 3, the gas barrier sheet 1 has the base material 2 and the anchor The adhesion between the film 9 and the adhesion between the anchor film 9 and the gas barrier film 3 are improved. In some cases, adhesiveness can be secured by inserting a predetermined film between the base material 2 and the anchor film 9 and between the anchor film 9 and the gas barrier film 3. As a method for estimating the degree of adhesion of the gas barrier film 3, the anchor film 9, the base material 2 and the like, for example, evaluation by a crosscut test can be given. In the present invention, the cross-cut test is performed in accordance with the description of JIS-K5400, 8.5.1. Specifically, using a cutter guide with a gap interval of 2 mm, cuts that reach the substrate 2 and the like through the gas barrier film 3 are vertically and horizontally formed into 100 grids, and cellophane adhesive tape (405 manufactured by Nichiban Co., Ltd.). No. 24mm width) is attached to the cut surface of the mass and rubbed with an eraser to completely adhere, and then peeled off vertically. Then, the surface after peeling is visually observed, and the layer residual ratio in 100 squares (the part peeled even in a part of the square is treated as the number of peeled) is used as a measure of adhesiveness, and the adhesiveness (%) = (1- (Peeled square / 100 square)) × 100 is calculated and evaluated.

  If the cross-cut test is performed both immediately after the gas barrier sheet production and after the heat and humidity resistance test, not only the adhesion of the gas barrier film 3, the anchor film 9, the base material 2 and the like in the state after production, The durability of this adhesiveness can also be evaluated. And as a method of a heat-and-moisture resistance test, for example, a thermo-hygrostat adjusted to an environment of temperature 60 ° C./humidity 95% RH is used, and the gas barrier sheet is held in the thermo-hygrostat for 1000 hours. be able to.

  The gas barrier sheet of the present invention is preferably used in the form of a film. By making it into a film form, it becomes easy to apply to uses such as an organic EL display. Moreover, the gas barrier sheet of the present invention can be used in the form of a take-up roll, and may be used as appropriate in accordance with a subsequent process of manufacturing an organic EL display or the like. The gas barrier sheet of the present invention can be used not only as a substrate for an organic EL display or the like, but also as a sealing film as an alternative to a sealing glass or can.

(Method for producing gas barrier sheet)
The method for producing the gas barrier sheet 1 is anchored using a polysiloxane polymer obtained by polymerizing a siloxane compound and a compound A having a functional group capable of reacting with a hydroxyl group of the siloxane compound at the time of polymerization. An anchor film forming step for forming (forming) the film 9 and a gas barrier film forming step for forming (forming) the gas barrier film 3 are included. Thereby, the gas barrier sheet | seat 1 can be manufactured favorably, As a result, the manufacturing method of the gas barrier sheet | seat 1 which is excellent in various characteristics, such as gas barrier property, can be provided.

  The details of the method of forming the anchor film 9 (anchor film forming step) are as already described in the detailed description of the anchor film 9. The method for forming the gas barrier film 3 (gas barrier film forming step) is also as already described in the detailed description of the gas barrier film 3. Therefore, in order to avoid duplication of explanation, explanation here is omitted.

  In the manufacturing method of the gas barrier sheet 1, steps other than the above steps may be appropriately performed. Examples of such other processes include a base material preparing process for preparing the base material 2, a transparent conductive film forming process for forming the transparent conductive film 4, a hard coat film forming process for forming the hard coat film 5, and a hygroscopic film. And a heat-dissipating gas barrier film forming step for forming the heat-dissipating gas barrier film 14. And the preparation method (base material preparation process) of the base material 2 is the detailed description about the said base material 2, and is as having demonstrated the case where the resin-made base materials 2 are used as an example. Similarly, the method of forming the transparent conductive film 4 (transparent conductive film forming step) is as already described in the detailed description of the transparent conductive film 4. The method for forming the hard coat film 5 (hard coat film forming step) is as already described in the detailed description of the hard coat film 5. Further, the method of forming the hygroscopic film 13 (the hygroscopic film forming step) is as already described in the detailed description of the hygroscopic film 13. The method for forming the heat dissipating gas barrier film 14 (heat dissipating gas barrier film forming step) is as already described in the detailed description of the heat dissipating gas barrier film 14. Therefore, in order to avoid duplication of explanation for each step, explanation here is omitted.

  As described above, according to the method for producing a gas barrier sheet of the present invention, a gas barrier sheet having excellent transparency, high heat resistance, hardly curling, and excellent gas barrier properties can be produced.

  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]
(Manufacture of gas barrier sheet)
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.

<Anchor film formation process>
The polysiloxane polymer coating solution was produced as follows. First, 10.01 g of formic acid was added little by little while stirring 61.16 g of ethanol to prepare an ethanol solution of formic acid. Next, this solution was heated to 40 ° C. under a nitrogen atmosphere, and 20.83 g of tetraethoxysilane (TEOS) and 3.03 g of dimethyl oxalate (Compound A) were added dropwise under reflux to form TEOS, Compound A, Was polymerized. After dripping, it was allowed to cool to room temperature to prepare a polysiloxane polymer coating solution. Then, a mixed solution of ethanol: methanol = 2: 1 was added to this coating solution, and diluted so that the weight ratio was 1: 1 (solid content concentration 5% by weight).

  This coating solution was applied onto a substrate by a die coating method to form a coating film of about 1 μm, and an anchor film was formed with a preheating of 60 ° C./1 minute and a thermosetting condition of 120 ° C./3 minutes.

<Gas barrier film formation process>
Next, an SiN _x O _y film having a thickness of 40 nm was formed on the anchor film by an ion plating method. The conditions for the ion plating method are as follows.

Deposition conditions:
Applied power 5.1kW
Vapor deposition material Silicon nitride Argon flow rate 15sccm
Oxygen flow rate 5sccm

  The characteristics of the gas barrier sheet having the gas barrier film prepared as described above were evaluated by the following methods.

(Analysis of composition: anchor film)
The composition of the anchor film (configuration and polymerization ratio of the polysiloxane polymer) was measured by XPS (ESCA LAB220i-XL apparatus 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 was performed using the software Eclipse version 2.1 attached to the above-described XPS apparatus, and using peaks corresponding to the binding energy of Si: 2p, C: 1s. 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. Then, the carbonyl bond peak other than the hydrocarbon peak position is compound A, the Si peak is a siloxane compound, Shirley background is removed for each peak, and the sensitivity coefficient of each element is corrected to the peak area (Si = 0.87 with respect to C = 1.0) was performed to determine the atomic ratio. As a result, the atomic ratio of Si was 50%, and the atomic ratio of carbonyl bonds was 10%. For this reason, it turned out that a polysiloxane polymer is comprised from TEOS (siloxane compound) and dimethyl oxalate (compound A). From the above measurement results, it can be considered that the polymerization ratio of TEOS and dimethyl oxalate is 50 mol% for TEOS and 5 mol% for dimethyl oxalate.

(Analysis of composition: gas barrier film)
The composition of the gas barrier film (values of x and _y in SiN _x O _y ), more specifically, the atomic ratio of Si, N, and O 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. Analysis after the measurement was performed using software Eclipse version 2.1 attached to the above-described XPS apparatus and using peaks corresponding to binding energies of Si: 2p, N: 1s, and O: 1s. At this time, the background of Shirley is removed for each peak, and the sensitivity coefficient correction of each element is performed on the peak area (Si = 0.87, N = 1.77, O = for C = 1.0). 2.85) was performed to determine the atomic ratio. About the obtained atomic ratio, the number of Si atoms was set to 1, and the number of atoms of N and O which are other components was calculated, and it was set as the component ratio. As a result, x = 1.10 and y = 0.20.

(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. In addition, although the detection limit of the water-vapor-permeability measuring apparatus used for the measurement is 0.05 g / m < ² > * day, when the water-vapor-permeation rate was measured, it was below the detection limit.

(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. In addition, although the detection limit of the oxygen gas permeability measuring apparatus used for the measurement is 0.05 cc / m ² · day · atm, when the oxygen permeability was measured, it was below the detection limit.

(Measurement of total light transmittance and color (YI))
The total light transmittance and YI of the gas barrier sheet were measured using SM color computer SM-C (manufactured by Suga Test Instruments). The measurement was performed according to JIS K7105. As a result, the total light transmittance was 85.6%, and Y1 was 0.6.

(Evaluation of curl)
The evaluation of the degree of curling was performed as follows. That is, the produced gas barrier sheet was cut into 15 cm × 15 cm to obtain a gas barrier sheet sample 10 shown in FIG. Then, as shown in the figure, the gas barrier sheet sample 10 was placed on the stainless steel substrate 6, and the orthogonal distance L between the vertex 8 of the gas barrier sheet sample 10 and the stainless steel substrate 6 was measured. And according to the magnitude | size of the orthogonal distance L, the generation | occurrence | production degree of the curl of a gas barrier sheet was evaluated on the following evaluation criteria. As a result, the evaluation was “◯”.

○: Orthogonal distance is 1 mm or less △: Orthogonal distance is 1 to 3 mm
X: The orthogonal distance is larger than 3 mm

  Next, a heat cycle test was performed on the gas barrier sheet sample 10, and the orthogonal distance L was measured again after the heat cycle test. The heat cycle test was performed by repeating the operation of holding the gas barrier sheet sample 10 in an oven at 150 ° C. for 3 hours and then cooling to room temperature five times. Then, the gas barrier sheet sample 10 after the heat cycle test is placed on the stainless steel substrate 6 again, and the orthogonal distance L between the apex of the gas barrier sheet sample 10 and the stainless steel substrate 6 is measured. The degree of curling of the gas barrier sheet was evaluated according to the above evaluation criteria according to the size of L. As a result, the evaluation was “◯”.

(Evaluation of extinction coefficient)
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. As a result, the extinction coefficient of the anchor film was 0.0001, and the extinction coefficient of the gas barrier film was 0.008.

(Adhesive evaluation)
The adhesion of the gas barrier sheet was evaluated by a cross cut test. Specifically, the evaluation was performed in accordance with the description of JIS-K5400, 8.5.1. That is, using a cutter guide with a gap interval of 2 mm, cuts reaching the base material through the gas barrier film were made vertically and horizontally to form 100 grids, and cellophane adhesive tape (No. 405, 24 mm width, manufactured by Nichiban Co., Ltd.) was used. After sticking on the cut surface of the shape and rubbing it completely with an eraser, it was peeled off vertically. Then, the surface after peeling is visually observed, and the layer residual ratio in 100 squares (the part peeled even in a part of the square is treated as the number of peeled) is used as a measure of adhesiveness, and the adhesiveness (%) = (1- (Peeled cells / 100 cells)) × 100 was calculated and evaluated.

  The cross-cut test was performed both immediately after the production of the gas barrier sheet and after the heat and humidity resistance test. The moisture and heat resistance test was performed by holding a gas barrier sheet for 1000 hours in an environment of a temperature of 60 ° C./humidity of 95% RH using a digital thermostat / humidifier PR-3K manufactured by Espec.

  As a result, the adhesiveness immediately after the production of the gas barrier sheet was 100%, and the adhesiveness after the wet heat resistance test was also 100%.

(Measurement of secondary particle size and distance between secondary particles)
The particle size of the secondary particles forming the gas barrier film and the distance between the secondary particles were measured. Specifically, Nanopics-1000 manufactured by Seiko Instruments Inc. was used, and the measurement was performed under the measurement conditions in which the observation mode was a contact mode, the scan range was 4 μm square, and the scan speed was 90 seconds / frame. Subsequently, arbitrary 30 points were set by trackball operation on analysis software installed on a personal computer or the like. And the least square method circle approximation was performed with respect to the point, and the average value was made into the secondary particle diameter. The distance between adjacent particles was determined by calculating the average value between the ends of the particles calculated by circular approximation. As a result, the particle size of the secondary particles was 450 nm, and the distance between the secondary particles was 210 nm.

[Comparative Example 1]
A gas barrier sheet was produced in the same manner as in Example 1 except that the gas barrier film was not provided. Of the evaluations performed in Example 1, the water vapor transmission rate, the oxygen transmission rate, and the total light transmittance and color (YI) were measured. As a result, the water vapor transmission rate was 1.2 g / m ² · day, the oxygen transmission rate was 3.4 cc / m ² · day · atm, the total light transmittance was 86.3%, and YI was -0.4 (blue). It became.

[Comparative Example 2]
A gas barrier sheet was produced in the same manner as in Example 1 except that the anchor film was not provided. And evaluation of adhesiveness was performed among the evaluation performed in Example 1. FIG. As a result, the adhesiveness immediately after production of the gas barrier sheet was 100%, and the adhesiveness after the wet heat resistance test was 95%.

[Comparative Example 3]
A gas barrier sheet was produced in the same manner as in Example 1 except that the anchor film was formed of an acrylic resin and that the thickness of the anchor film was 3 μm. Specifically, the following resin composition was applied with wire bar # 10, and then irradiated with 300 mJ of ultraviolet rays to form an anchor film.
<UV curable resin composition>
Ethylene glycol di (meth) acrylate 50 parts Photopolymerization initiator (Irgacure 184: manufactured by Ciba Geigy) 5 parts Solvent (toluene) 50 parts

  Of the evaluations performed in Example 1, the water vapor transmission rate, the oxygen transmission rate, and the total light transmittance and color (YI) were measured. As a result, the water vapor transmission rate was below the detection limit, the oxygen transmission rate was below the detection limit, the total light transmittance was 80.6%, and YI was 5.4. As can be seen from the value of YI, the gas barrier sheet was colored yellow. This is because the anchor bond of the acrylic resin anchor film is increased by the heat treatment during manufacturing, and the blue component in the visible light is absorbed and yellowed.

[Example 2]
Using the gas barrier sheet of Example 1, the surface of the base material on which the anchor film and the gas barrier film (SiN _x O _y film) are not formed is ion-plated to form a 40 nm thick surface. A gas barrier sheet was manufactured by further providing a backside gas barrier film (SiN _x O _y film) and a transparent conductive film having a thickness of 30 nm. The conditions for the ion plating method are as follows.

Deposition conditions for the back side gas barrier film:
Applied power 5.1kW
Vapor deposition material SiO _x N _y (x = 0.1, y = 1.0)
Argon flow rate 15sccm
Oxygen flow rate 5sccm

Film formation conditions for transparent conductive film:
Material: ITO grain (15% Sn)
Film forming pressure: 0.1 Pa
Ar flow rate: 10 sccm, oxygen flow rate: 10 sccm
Applied power: 4.0 kW

When the surface resistance value and thermal conductivity of the obtained transparent conductive film were measured, they were 1.5 × 10 ⁴ Ω / □ and 4 W / mK, respectively. The surface resistance value was measured using Hiresta UP (MCP-HT450), which is a high resistivity meter manufactured by Dia Instruments Co., Ltd. Moreover, the thermal conductivity of the transparent conductive film was measured using a steady-state thermal conductivity measuring device GH series manufactured by ULVAC-RIKO.

The characteristics of the gas barrier sheet prepared as described above were evaluated in the same manner as in Example 1. In addition, unlike Example 1, the water vapor transmission rate was measured using an apparatus capable of measuring up to a higher measurement limit (0.5 mg / m ² / day). As a result, the composition of the back side gas barrier film was x = 1.0 and y = 0.15 in SiN _x O _y . Other characteristics are as follows.

Water vapor transmission rate: 0.0015 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 78.5%
YI: 3.8
Curl evaluation: “O” before and after heat cycle test
Extinction coefficient of backside gas barrier film: 0.005
Evaluation of adhesiveness: 100% immediately after production, 100% after wet heat resistance test

[Example 3]
A gas barrier sheet was produced in the same manner as in Example 2 except that the conditions for forming the transparent conductive film by the ion plating method were as follows.

Film formation conditions for transparent conductive film:
Material: ITO grain (20% Sn)
Film forming pressure: 0.1 Pa
Ar flow rate: 10 sccm, oxygen flow rate: 20 sccm
Applied power: 4.0 kW

When the surface resistance value and thermal conductivity of the obtained transparent conductive film were measured, they were 4.3 × 10 ⁵ Ω / □ and 8 W / mK, respectively.

  For the gas barrier sheet prepared as described above, the same anchor film, gas barrier film, and backside gas barrier film as those in Example 2 were used. For this reason, the extinction coefficient of the back-side gas barrier film has the same value as in Example 2. Therefore, other characteristics were evaluated in the same manner as in Example 2. The water vapor transmission rate was also measured in the same manner as in Example 2. The results are shown below.

Water vapor transmission rate: 0.0021 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 78.1%
YI: 3.7
Curl evaluation: “O” before and after heat cycle test
Evaluation of adhesiveness: 100% immediately after production, 100% after wet heat resistance test

[Comparative Example 4]
An attempt was made to produce a gas barrier sheet in the same manner as in Example 1 except that the anchor film was formed of a polysiloxane polymer composed only of TEOS without using Compound A. Specifically, a solution in which 18.01 g of pure water was added to 32.04 g of methanol was prepared. Next, this solution was heated to 80 ° C. under a nitrogen atmosphere, and 20.83 g of TEOS was added dropwise under reflux, followed by stirring for 1 hour to prepare a coating solution. Using this coating solution, an attempt was made to form a coating film on a substrate by spin coating. However, since no polymerizing agent was contained, the polymer was spontaneously polymerized by moisture, and particles were generated on the coated surface or uneven film thickness. As a result, gas barrier sheets could not be produced.

[Example 4]
Production of gas barrier sheet in the same manner as in Example 1 except that the anchor film was formed of a polysiloxane polymer composed of TEOS: 76.9 mol% and dimethyl malonate (Compound A): 23.1 mol%. Tried. Below, the difference with Example 1 is demonstrated about the manufacturing method of a gas barrier property sheet | seat.

  Specifically, a polysiloxane polymer coating solution was produced as follows. First, 10.01 g of formic acid was added little by little while stirring 61.16 g of ethanol to prepare an ethanol solution of formic acid. Next, this solution was heated to 40 ° C. under a nitrogen atmosphere, and 20.83 g of TEOS and 3.39 g of dimethyl malonate (Compound A) were added dropwise under reflux to polymerize TEOS and dimethyl malonate. . After dripping, it was allowed to cool to room temperature to prepare a polysiloxane polymer coating solution. Then, a mixed solution of ethanol: methanol = 1: 1 was added to this coating solution, and diluted so that the weight ratio was 1: 1 (solid content concentration 5% by weight).

  This coating solution was applied onto a substrate by a die coating method to form a coating film of about 1 μm, and an anchor film was formed with a preheating of 60 ° C./1 minute and a thermosetting condition of 150 ° C./15 minutes.

  For the gas barrier sheet obtained as described above, first, the secondary particle diameter of the gas barrier film and the distance between the secondary particles were measured in the same manner as in Example 1. As a result, the particle size of the secondary particles was 350 nm, and the distance between the secondary particles was 140 nm. Next, the same evaluation as in Example 1 was performed for various types of identification. The water vapor transmission rate was measured in the same manner as in Example 2. The results are shown below.

Water vapor transmission rate: 0.0065 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 85.0%
YI: 1.5
Curl evaluation: “O” before and after heat cycle test
Anchor film extinction coefficient: 0.01
Adhesive evaluation: 100% immediately after production, 95% after wet heat resistance test

[Example 5]
Using the gas barrier sheet of Example 1, a transparent conductive film having a thickness of 30 nm is formed by ion plating on the surface of the substrate on which the anchor film and the gas barrier film (SiN _x O _y film) are formed. Was further provided to produce a gas barrier sheet. The conditions for the ion plating method are as follows.

Film formation conditions for transparent conductive film:
Material: ITO grain (15% Sn)
Film forming pressure: 0.1 Pa
Ar flow rate: 10 sccm, oxygen flow rate: 10 sccm
Applied power: 4.0 kW

When the surface resistance value and thermal conductivity of the obtained transparent conductive film were measured in the same manner as in Example 2, they were 1.5 × 10 ⁴ Ω / □ and 4 W / mK, respectively.

  The characteristics of the gas barrier sheet prepared as described above were evaluated in the same manner as in Example 1. The water vapor transmission rate was measured in the same manner as in Example 2. Various characteristics are shown below.

Water vapor transmission rate: 0.0008 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 79.6%
YI: 3.2
Curl evaluation: “O” before and after heat cycle test
Evaluation of adhesiveness: 100% immediately after production, 100% after wet heat resistance test

[Example 6]
Using the gas barrier sheet of Example 1, a gas barrier sheet was produced by further providing a 100 nm thick hygroscopic film formed of strontium oxide on the gas barrier film by an ion plating method. The conditions for the ion plating method are as follows.

Conditions for forming a hygroscopic film:
Material: Strontium oxide grains Filming pressure: 0.3 Pa
Ar flow rate: 20 sccm, oxygen flow rate: 5 sccm
Applied power: 5.0 kW

  The characteristics of the gas barrier sheet prepared as described above were evaluated in the same manner as in Example 1. The evaluation of the extinction coefficient of the hygroscopic film was also performed in the same manner as the method of evaluating the extinction coefficient of the anchor film and the gas barrier film in Example 1. Various characteristics are shown below.

Water vapor transmission rate: 0.05 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 90.1%
YI: 0.2
Curl evaluation: “O” before and after heat cycle test
Absorption coefficient of moisture absorption film: 1 × 10 ⁻⁵
Evaluation of adhesiveness: 100% immediately after production

[Example 7]
Using the gas barrier sheet of Example 1, a heat-dissipating gas barrier film having a thickness of 50 nm formed from diamond-like carbon (DLC) is provided on the gas barrier film by ion plating, and further on the heat-dissipating gas barrier film. A gas barrier sheet was produced by providing a hygroscopic film with a thickness of 100 nm formed from strontium oxide by an ion plating method. The conditions for forming the heat-dissipating gas barrier film are as follows. The conditions for forming the hygroscopic film were the same as in Example 6.

Deposition conditions of heat dissipation gas barrier film:
Material: Ethylene gas Pressure during film formation: 0.1 Pa
Ar flow rate: 20 sccm, ethylene flow rate: 15 sccm
Applied power: 5.0 kW

  In addition, when the heat radiating gas barrier film was formed during the production of the gas barrier sheet, the thermal conductivity of the heat radiating gas barrier film was measured. As a result, it was 35 W / mK. The thermal conductivity of the heat-dissipating gas barrier film is measured by using a laser alternating current method thermal diffusivity measuring device LaserPIT-1 manufactured by ULVAC-RIKO Co., Ltd. It was measured.

  The characteristics of the gas barrier sheet prepared as described above were evaluated in the same manner as in Example 1 (the extinction coefficient of the hygroscopic film was the same value as in Example 6). Various characteristics are shown below.

Water vapor transmission rate: 0.05 g / m ² · day
Oxygen permeability: 0.05 cc / m ² · day · atm
Total light transmittance: 89.8%
YI: 0.3
Curl evaluation: “O” before and after heat cycle test
Evaluation of adhesiveness: 100% immediately after production

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 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 the method of measuring the degree of curl of a gas barrier sheet. 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 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 gas barrier sheet | seat of this invention.

Explanation of symbols

1, 1A, 1B, 1C, 1D, 1E, 1F, 1G, 1H, 1I Gas barrier sheet 2 Base material 3, 3A, 3B, 3C, 3D Gas barrier film 4 Transparent conductive film 5 Hard coat film 6 Substrate made of stainless steel 8 apex 9, 9A, 9B anchor film 10 gas barrier sheet sample 11 one side 12 other side 13 hygroscopic film 14 heat dissipating gas barrier film

Claims (14)

In a gas barrier sheet having a base material, an anchor film provided on one side of the base material, and a gas barrier film provided on the anchor film,
The anchor film is a siloxane compound, methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl valerate, dimethyl oxalate, dimethyl malonate, dimethyl oxalate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, Containing a polysiloxane polymer composed of compound A which is at least one of ethyl valerate, diethyl oxalate, diethyl malonate, and diethyl oxalate ;
The gas barrier sheet, wherein the gas barrier film is a SiN _x O _y film (where x = 0.5 to 1.5, y = 0.15 to 1).   The gas barrier sheet according to claim 1, wherein the polysiloxane polymer is composed of 70 mol% to 99 mol% of the siloxane compound and 1 mol% to 30 mol% of the compound A.   The gas barrier sheet according to claim 1 or 2, wherein the anchor film has an extinction coefficient of 0.00001 to 0.01.   The gas barrier sheet according to any one of claims 1 to 3, wherein the extinction coefficient of the gas barrier film is 0.000001 to 0.01.   The gas barrier sheet according to any one of claims 1 to 4, wherein the anchor film is provided also on the other surface side of the base material, and the gas barrier film is provided on the anchor film.   The gas barrier sheet according to claim 1, comprising a transparent conductive film on the gas barrier film.   The gas barrier sheet according to claim 1, wherein a hard coat film is provided on at least one side of the gas barrier sheet.   The gas barrier sheet according to any one of claims 1 to 7, wherein the gas barrier film is formed by aggregation of secondary particles, and the particle size of the secondary particles is from 300 nm to 1500 nm.   The gas barrier sheet according to claim 8, wherein a distance between adjacent secondary particles is 100 nm or more and 300 nm or less.   The gas barrier sheet according to any one of claims 1 to 9, further comprising a moisture absorption film formed of a material B capable of adsorbing and desorbing moisture and maintaining a solid state even when moisture is adsorbed.   The gas barrier sheet according to claim 10, wherein the material B is an alkali metal oxide or an alkaline earth metal oxide. The gas barrier sheet according to claim 10 or 11, wherein the moisture absorption film has an extinction coefficient of 1 x ^10-6 to 1 x ^10-3 .   The gas barrier sheet according to any one of claims 10 to 12, further comprising a heat dissipating gas barrier film. It is a manufacturing method of the gas barrier property sheet according to any one of claims 1 to 13,
Siloxane compounds and methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl valerate, dimethyl oxalate, dimethyl malonate, dimethyl oxalate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, oxalic acid An anchor film forming step of forming an anchor film using a polysiloxane polymer obtained by polymerizing Compound A which is at least one of diethyl, diethyl malonate, and diethyl oxalate;
A gas barrier film forming step of forming a gas barrier film;
A method for producing a gas barrier sheet, comprising:

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