JP5012272B2 - Gas barrier sheet - Google Patents

Description

  The present invention relates to a gas barrier sheet, and more particularly, to a gas barrier sheet having high productivity, hardly curling, and excellent gas barrier properties.

  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. For example, Patent Document 1 discloses a cured product of a UV curable resin containing only an acrylic monomer and / or an acrylic polymerizable prepolymer as a polymerization component on one or both sides 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.
Japanese Patent Laying-Open No. 2005-313560 (Claim 1, Paragraph 0012, Paragraph 0039)

  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, from the viewpoint of further improving the productivity of the gas barrier sheet, there is a problem that it is desired to achieve both gas barrier properties and curl generation suppression with only the gas barrier film.

  Further, the gas barrier sheet is expected to be applied to an organic EL display. An organic EL display is expected to be a next-generation flat panel display because it is thin, variable in shape, and flexible, but has a problem that it is weak against moisture. Specifically, when moisture or oxygen penetrates from defects such as pinholes existing on the cathode surface of an organic EL display, an area that does not emit light is generated due to oxidation of the cathode metal or interface peeling between the cathode metal and the organic compound. At the same time that the brightness is lowered. The areas that do not emit light are generally called dark spots or black spots, but in order to suppress the generation of such dark spots and black spots and ensure display quality, the entry of moisture and oxygen into the organic EL display is suppressed. There is a need to. For this reason, application of a gas barrier sheet to an organic EL display has been attempted.

  In applying a gas barrier sheet to an organic EL display, a high level of gas barrier property is required from the viewpoint of ensuring good display quality of the organic EL display. Specifically, gas barrier properties of 1/100 or 1/1000 or less are required as compared with food-related fields in which gas barrier sheets are generally used. Therefore, in order to satisfactorily apply to an organic EL display, it is necessary to develop a gas barrier sheet having a higher level of gas barrier than conventional ones.

  In addition, the organic EL display has a heat cycle test as one of its durability evaluation tests. The heat cycle test is a test for evaluating the durability of the organic EL display by repeatedly holding it at a high temperature for a certain period of time, but also in a gas barrier sheet provided in contact with the organic EL display for suppressing intrusion of moisture and the like. Thus, it is desirable that no curl deformation or the like or a gas barrier property decrease when such a heat cycle test is performed.

  The present invention has been made in order to solve the above-mentioned problems, and its purpose is to achieve high productivity, good gas barrier properties, curl generation, and high gas barrier film adhesion. To provide a sheet. 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 wondered whether sialon could be adopted as a gas barrier film in the course of research and development of a gas barrier sheet having excellent denseness and flexibility without using a UV curable resin film such as an acrylic resin. Sialon is an engineering ceramic represented by Si-Al-O-N, but has a high heat resistance and tends to be a dense structure, and is used as an additive for sintered bodies used for gas turbine engine members, for example. (Japanese Patent Laid-Open No. 6-293666). Under the assumption that these properties can be applied to the gas barrier film, the present inventors have intensively studied, and as a result, the gas barrier film using sialon further improved the composition, so that the gas barrier film alone The present inventors have found that gas barrier properties can be increased and curling can be suppressed.

The gas barrier sheet of the present invention for solving the above problems is a gas barrier sheet having a gas barrier film on a substrate, wherein the gas barrier film is a SiN _s M _t O _u C _v film (where s = 0.5 ˜1.5, t = 0.01 to 0.3, u = 0.25 to 1, v = 0 to 1, and M is Al and / or Mg).

According to the present invention, the gas barrier _{film, SiN s M t O u C} v film (where, s = 0.5~1.5, t = 0.01~0.3 , u = 0.25~1, v = 0 to 1 and M is Al and / or Mg.) Therefore, a film having a dense sialon composition can be formed, and a gas barrier film alone can ensure good gas barrier properties, and a predetermined amount of oxygen can be obtained. Introducing carbon makes it difficult for curling to occur, and by introducing carbon, the adhesive strength with the substrate can be increased, resulting in high productivity, good gas barrier properties, and curling is suppressed. Furthermore, it is possible to provide a gas barrier sheet with high adhesion of the gas barrier film. In particular, it is possible to provide a gas barrier sheet in which curling is suppressed and gas barrier performance is maintained even after a heat cycle test performed as a durability test for an organic EL display or the like.

  In a preferred embodiment of the gas barrier sheet of the present invention, v is 0, and the refractive index of the gas barrier film is 1.5 to 2.0.

According to the present invention, v is 0, since the refractive index of the gas barrier film is 1.5 to _2.0, the density of the gas barrier film in the case where SiN _s M _t O u _{C v} film carbon not introduced Since it becomes easy to ensure favorable gas barrier property by making it high, as a result, a gas barrier property sheet with favorable gas barrier property can be provided.

  In a preferred embodiment of the gas barrier sheet of the present invention, the v is 0.1 to 1, and the refractive index of the gas barrier film is 1.8 to 2.2.

According to the present invention, v is 0.1 to 1, the refractive index of the gas barrier film is 1.8 to _2.2, the gas barrier in the case of introducing carbon into the SiN _s M _t O u _{C v} film Since it becomes easy to ensure good gas barrier property by increasing the density of the film, as a result, it is possible to provide a gas barrier sheet having good gas barrier property while further improving the adhesiveness of the gas barrier film.

  In a preferred embodiment of the gas barrier sheet of the present invention, the extinction coefficient of the gas barrier film is 0.000001 or more and 0.03 or less.

  According to this invention, since the extinction coefficient of the gas barrier film is 0.000001 or more and 0.03 or less, it becomes easy to ensure the transparency of the gas barrier film, and as a result, a highly transparent gas barrier sheet is obtained. Can do.

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

  According to the present invention, since the transparent conductive film is provided on the gas barrier film, the transparent conductive film can be used as an anode of the organic EL display, and as a result, the productivity of the organic EL display is improved. Can do.

  In a 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 this 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 possible to provide a gas barrier sheet that is not easily damaged. it can.

  In a preferred embodiment of the gas barrier sheet of the present invention, an anchor coat agent film is provided between the base material and the gas barrier film, and the anchor coat agent film comprises a cardo polymer, a polyfunctional acrylic resin, a layered compound, and At least one of a composition comprising a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having a second organic functional group that reacts with the organic functional group as raw materials. contains.

  According to the present invention, an anchor coat agent film is provided between the base material and the gas barrier film, and the anchor coat agent film comprises a cardo polymer, a polyfunctional acrylic resin, a layered compound, and an organic functional group and a hydrolyzable group. Since it contains at least one of the composition comprised from the silane coupling agent which has this, and the crosslinking | crosslinked compound which has a 2nd organic functional group which reacts with the organic functional group which a silane coupling agent has, as a raw material The adhesion between the gas barrier film and the substrate can be improved, and as a result, a gas barrier sheet with high adhesion can be obtained.

  According to the gas barrier sheet of the present invention, it is possible to provide a gas barrier sheet having high productivity, good gas barrier properties, curling occurrence, and high gas barrier film adhesion. In particular, it is possible to provide a gas barrier sheet in which curling is suppressed and gas barrier performance is maintained even after a heat cycle test performed as a durability test for an organic EL display or the like.

  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. 5 is a schematic cross-sectional view showing still another example of the gas barrier sheet, and FIG. 5 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 has a form of a gas barrier sheet 1 </ b> A having a gas barrier film 3 on a substrate 2. Further, as shown in FIG. 2, the gas barrier sheet 1 of the present invention has a form of a gas barrier sheet 1B having a gas barrier film 3 on a substrate 2 and further having a transparent conductive film 4 on the gas barrier film 3. You can also Furthermore, 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 1 </ b> C has the gas barrier film 3 and the transparent conductive film 4 in this order on the base material 2, and the surface opposite to the surface on which the gas barrier film 3 is formed of the base material 2. A hard coat film 5 is provided. In the gas barrier sheet 1A, the base material 2 and the gas barrier film 3 are provided in contact with each other. However, a single film such as an anchor coating agent film or a smoothing film is provided between the base material 2 and the gas barrier film 3. A plurality of them may be provided. Actually, the gas barrier sheet 1 </ b> D shown in FIG. 5 is obtained by providing an anchor coating agent film 9 between the base material 2 and the gas barrier film 3. Similarly, films such as an anchor coat agent film and a smoothing film are used as the interface between the base material 2 and the gas barrier film 3 of the gas barrier sheets 1B and 1C, the interface between the gas barrier film 3 and the transparent conductive film 4, and the base material 2. It can also be provided at the interface with the hard coat film 5. Further, in the gas barrier sheet 1C, the hard coat film 5 may be provided on the transparent conductive film 4 side. 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 Konicakat KC4UX, KC8UX, etc.) And commercially available products such as polyethylene naphthalate film (for example, Teonex (registered trademark) of Teijin DuPont Films Ltd.).

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

  When the 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 transparent. By making other films such as the gas barrier film 3 transparent together with the substrate 2, the gas barrier sheets 1A, 1B, 1C, and 1D 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 preferably has a predetermined smoothness. Specifically, the arithmetic average roughness (Ra) of the surface of the substrate 2 is usually set to 0.3 nm or more. If it is this range, moderate surface roughness can be provided to the base material 2, and when the base material 2 is used as a take-up roll, slippage hardly occurs on the contact surfaces of the base materials 2 that are in contact with each other. The arithmetic average roughness (Ra) of the surface of the substrate 2 is usually 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. If it is this range, the smoothness of the base material 2 will improve and it will become easy to exhibit the advantage which can suppress the short circuit which may generate | occur | produce when producing display elements, such as an organic EL display. The arithmetic average roughness (Ra) may be measured according to JIS B 0601-2001 (based on ISO 4287-1997).

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

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

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

(Gas barrier film)
In the gas barrier film _{3, SiN s M t O u} C v film (where, s = 0.5~1.5, t = 0.01~0.3 , u = 0.25~1, v = 0~ 1, M is Al and / or Mg).

  By using the gas barrier film 3 described above, a film having a dense sialon composition can be formed so that a good gas barrier property can be secured by the gas barrier film 3 alone, and curling is less likely to occur due to the introduction of a predetermined amount of oxygen. Since carbon can increase the adhesive strength with the substrate 2 and the like, as a result, the productivity is high, the gas barrier property is good, the occurrence of curling is suppressed, and the adhesion of the gas barrier film 3 is further improved. High gas barrier sheets 1A, 1B, 1C, and 1D can be provided. In particular, it is possible to provide the gas barrier sheets 1A, 1B, 1C, and 1D 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.

In _SiN s _M t _O u _{C v} film used for the gas barrier film 3, s = 0.5~1.5, t = 0.01~0.3, u = 0.25~1, v = 0~1 , M is Al and / or Mg. s is 0.5 or more, preferably 0.7 or more, and 1.5 or less, preferably 1.3 or less. Since the Si—N bond in the gas barrier film 3 has an action of suppressing the permeation of moisture and oxygen, the amount of Si—N bond in the gas barrier film 3 is ensured by setting s to the above range, and the gas barrier film 3 It becomes easy to improve the gas barrier property. t is 0.01 or more, preferably 0.03 or more, and 0.3 or less, preferably 0.2 or less. Within the above range, aluminum oxide, magnesium oxide, or a composite oxide of aluminum and magnesium is easily dissolved in silicon nitride (Si ₃ N ₄ ), and the denseness of the gas barrier film 3 is easily secured. u is 0.25 or 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. By adopting such a composition, it becomes easy to balance the denseness that contributes to securing the gas barrier property and the flexibility that contributes to suppressing the occurrence of curling, and the occurrence of cracks in the gas barrier film 3 and the base material against heating and cooling stress. Peeling from 2 etc. is suppressed. As a result, the occurrence of curling is easily suppressed even after the heat cycle test, and the deterioration of the gas barrier property is easily suppressed.

Although v in _SiN s _M t _O u _{C v} film used for the gas barrier film 3 is 0 or more, preferably 0.01 or more, more preferably 0.1 or more, also 1 or less, preferably 0.7 or less, And When the above-mentioned range, the introduction of carbon SiN _s M _t O _u C _v film, ensuring adhesion between the gas barrier film 3 and the substrate 2 or the like is easily performed. That is, the carbon which is introduced into the SiN _s M _t O _u C _v film, specifically, lower hydrocarbons and alcohols, ketones, can be mentioned acetaldehyde, and the like. And it is estimated that such carbon is couple | bonded around Si or O as organic functional groups, such as an alkyl group, an alkoxy group, a ketone group, an acetaldehyde group, for example. For this reason, for example, when a resin film is used for the base material 2, the interaction between the organic functional group and the base material surface is strengthened, and the adhesive strength between the gas barrier film 3 and the base material 2 is improved. it is conceivable that. By increasing the adhesive strength between the gas barrier film 3 and the base material 2 and the like, the gas barrier film 3 becomes more difficult to peel from the base material 2 and the like due to heat stress of heating and cooling. Generation | occurrence | production becomes easy to be suppressed and the fall of gas barrier property is also easy to be suppressed.

SiN _s M _t O _u C _v film, as described above, tends to increase the adhesion between the gas barrier film 3 and the substrate 2 or the like by the introduction of carbon. This is the introduction of carbon into SiN _s M _t O _u C _v film, and an organic functional group of the resin used for the base material, this means that the organic functional groups capable of undergoing a covalent bond or a dehydration condensation reaction is introduced It is guessed.

However, even when the SiN _s M _t O _u C _v film without introducing carbon (v = 0), adhesion between the gas barrier film 3 and the substrate 2 is improved by the base material 2 made of resin It becomes a trend. For example, when the substrate 2 is formed of a polyester resin, bond length between the carbon-oxygen having a polyester _{resin, SiN s M t O u C} v is present in the film, Si-O, Mg as Mg-O (M ), The bond distance between the gas barrier film 3 and the substrate 2 tends to be improved due to the interaction between the Si-N bond distances.

_In the case of using SiN _s M _t O u _{C v} film, the reason for improving the adhesion between the gas barrier film 3 and the substrate 2 or the like is one more. It tends to temperature, such as the substrate 2 is increased in depositing the elements constituting the SiN _s M _t O _u C _v film on the substrate 2 or the like, of these elements and the substrate 2 or the like to deposit interaction increases result is that the adhesion to the gas barrier film _{3 (SiN s M t O u} C v film) across the substrate 2 or the like tends to increase.

Such gas barrier film 3 and _{(SiN s M t O u C} v film) as a method of estimating the degree of adhesion between the substrate 2 and the like, for example, the adhesion between the gas barrier film 3 and the substrate 2 or the like by the cross cut method An evaluation can be given. In this invention, it carried out based on description of 8.5.1 of JIS-K5400. 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. 24 mm width) was attached to the cut surface of the mass and rubbed with an eraser to completely adhere, and then peeled off vertically. The surface after peeling was visually observed, and the layer residual ratio in 100 squares (the part that was peeled off even if part of the squares was treated as the number of peeled) was taken as a measure of adhesiveness, and adhesiveness (%) = (1 -(Peeled squares / 100 squares)) x 100 was calculated and evaluated. If the test by such a cross-cut method is performed both immediately after the gas barrier sheet production and after the moisture and heat resistance test described later, not only the adhesion of the gas barrier film 3 to the substrate 2 and the like in the state after the production, It becomes possible to evaluate the durability of the adhesiveness.

M in _SiN s _M t _O u _{C v} film used for the gas barrier layer 3 is the Al and / or Mg, the ease of formation of solid solution for sialon, from the viewpoint of maintaining the denseness, be Al or Mg Is preferred. Here, when M is composed of Al and Mg, the sum of the atomic ratio of Al and the atomic ratio of Mg is the value of t. By dissolving a metal oxide such as aluminum oxide or magnesium oxide into the SiN film, the Si-N bond that is strong but brittle, and the Mg-O bond that is weak in scratch resistance but highly flexible can be used. It can have both characteristics of Al-O bond. As a result, the gas barrier film 3 can follow the expansion and contraction of the base material 2 that occurs in the moisture and heat resistance test and the heat cycle test.

  The gas barrier film 3 may contain elements and substances other than Si, M, N, O, and C as impurities and additives as long as they are within the scope of the present invention.

The gas barrier film 3, is whether a predetermined _SiN s _M t _O u _{C v} film, for example, can be confirmed by obtaining Si, N, M, O, and an atomic ratio of C. 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 binding of Si: 2p, N: 1s, Al: 2p, Mg: 2p, O: 1s, C: 1s This is done using a peak corresponding to energy. 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. Shirley background was removed for each peak, and sensitivity coefficient correction for each element was made in the peak area (Si = 0.87, N = 1.77, Al = 0.67 for C = 1.0). , Mg = 0.36, O = 2.85) to obtain the atomic ratio. The carbon in this case is calculated excluding the peak attributed to the hydrocarbon. About the obtained atomic ratio, the number of Si atoms is set to 1, and the number of atoms of N, M, O, and C which are other components is calculated, and it is set as a component ratio.

_SiN s _M t _O u _{C v} film of the gas barrier film 3 is preferably divided into two compositions. The first composition is a gas barrier film 3A that does not introduce carbon when v = 0, and the second composition is a gas barrier film 3B that actively introduces carbon when v = 0.1-1. It is to be. And in gas barrier film 3A, 3B, it is preferable to control a refractive index as follows respectively.

The refractive index of the gas barrier film 3A is preferably 1.5 to 2.0. Since the refractive index is a value reflecting the density of the gas barrier film 3A, the density of the gas barrier film 3A can be increased by increasing the refractive index. If the density of the gas barrier film 3A can be increased, the permeability of oxygen and water vapor can be lowered and the gas barrier property can be improved. Thus, by controlling the refractive index of the gas barrier film 3A in the above _{range, SiN s M t O u C} v film good gas barrier properties by increasing the density of the gas barrier film 3A when the carbon is not introduced is easy to ensure the As a result, it is possible to provide gas barrier sheets 1A, 1B, 1C, 1D having good gas barrier properties.

  The gas barrier film 3A has a refractive index of 1.5 or more, preferably 1.7 or more. By setting it as the said range, the density of gas barrier film 3A can be ensured and permeation | transmission of oxygen and water vapor | steam can be suppressed now. On the other hand, from the viewpoint of securing gas barrier properties, it is preferable to increase the refractive index because it is preferable to increase the density of the gas barrier film 3A. However, as the refractive index increases, the film quality of the gas barrier film 3A tends to become harder. When the refractive index is excessively large, the flexibility of the gas barrier sheets 1A, 1B, 1C, and 1D becomes insufficient. For this reason, a refractive index shall be 2.0 or less.

On the other hand, the refractive index of the gas barrier film 3B is preferably 1.8 to 2.2. This is because, as described in the gas barrier film 3A, the gas barrier property is secured by setting the density of the gas barrier film 3B in a desired range. However, since carbon is introduced with v = 0.1 to 1 in the gas barrier film 3B, it is easy to ensure adhesion between the gas barrier film 3B and the base material 2 or the like. Thus, by controlling the refractive index of the gas barrier film 3B in the above range, good gas barrier properties by increasing the density of the gas barrier film becomes easy to secure in the case of introducing carbon SiN _s M _t O _u C _v film As a result, it is possible to provide a gas barrier sheet having a good gas barrier property while further improving the adhesion of the gas barrier film.

  The refractive index of the gas barrier film 3B is 1.8 or more, but preferably 1.9 or more. By setting it as the said range, the density of gas barrier film 3B can be ensured and permeation | transmission of oxygen and water vapor | steam can be suppressed now. On the other hand, from the viewpoint of securing gas barrier properties, it is preferable to increase the refractive index because it is preferable to increase the density of the gas barrier film 3B. However, as the refractive index increases, the film quality of the gas barrier film 3B tends to become harder. When the refractive index is excessively large, the flexibility of the gas barrier sheets 1A, 1B, 1C, and 1D becomes insufficient. For this reason, a refractive index shall be 2.2 or less.

Note that the preferable refractive index range of the gas barrier film 3B is 1.8 to 2.2 as compared with the preferable refractive index range 1.5 to 2.0 of the gas barrier film 3A, which is higher than that of the gas barrier film 3A. High value. This is _because, in the SiN _s M _t O u _{C v} film is divided to be introduced carbon, since the density is high.

  For the measurement of the refractive index in the gas barrier films 3A and 3B, a conventionally known method can be used, for example, an ellipsometer can be used. In the present invention, the refractive index is measured by UVISELTM 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 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 within the above range, the gas barrier film 3 alone can easily achieve both gas barrier properties and curl generation suppression.

  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 sheets 1A, 1B, 1C, and 1D 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 0.03 or less. The extinction coefficient is more preferably 0.000005 or more, further preferably 0.00001 or more, more preferably 0.01 or less, and further preferably 0.005 or less. By setting the extinction coefficient within the above range, it becomes easy to ensure the transparency of the gas barrier film 3, and as a result, the highly transparent gas barrier sheet 1 can be obtained.

  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 preferably insulating. Specifically, when the gas barrier sheet 1 is used as a display substrate or a sealing film for a display such as an organic EL display, the gas barrier film 3 is used to suppress a short circuit between the cathode and the anode of the display. Is preferably insulative. More specifically, the surface resistance value of the gas barrier film 3 is preferably 10 ¹⁰ Ω / □ or more, and more preferably 10 ¹¹ Ω / □ or more. Further, the surface resistance value is preferably as high as possible, but is usually 10 ¹⁶ Ω / □ or less.

  The surface resistance value in the gas barrier film 3 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. Can be measured.

  The method for producing the gas barrier film 3 is not particularly limited, and for example, a vacuum deposition 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.

  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 forming a mixture or complex oxide. 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).

Gas barrier layer _{3, SiN s M t O u C} v film (where, s = 0.5~1.5, t = 0.01~0.3 , u = 0.25~1, v = 0~1 Although M is to be Al and / or _Mg.), control of the composition of the SiN _s M _t O u _{C v} film, while using as appropriate the manufacturing method described above introduced, by changing the production conditions appropriate It can be carried out.

Specifically, in the case of using an ion plating method may be a method obtained by firing a raw material powder having the same composition as SiN _s M _t O _u C _v film. In this case, when it is necessary to control the atomic ratio of oxygen of the composition to be used, the raw material powder may be fired under a predetermined concentration of oxygen. When it is necessary to control the atomic ratio of nitrogen having a composition to be used, the raw material powder may be fired in the presence of nitrogen or ammonia at a predetermined concentration. Furthermore, when it is necessary to control the atomic ratio of carbon having a composition to be used, the raw material powder may be fired under a carbon compound having a predetermined concentration. Here, examples of the carbon compound include carbon compounds having 1 to 6 carbon atoms. More specifically, examples thereof include saturated hydrocarbons such as methane, ethane, propane, and butane, and unsaturated hydrocarbons such as ethylene, propylene, butylene, and acetylene.

As another method in the case of using the ion plating method, there is a method using reactive ion plating. More specifically, oxygen gas and / or nitrogen gas, or ammonia and / or lower hydrocarbons are flowed and combined with evaporated particles using plasma to synthesize a desired SiN _s M _t O _{u Cv} film. Just do it. In order to adjust the composition ratio of oxygen and nitrogen, nitrous oxide (N ₂ O), nitric oxide (NO), nitrogen dioxide (NO ₂ ), and dinitrogen tetroxide (N ₂ O ₄ ) may be used as appropriate. Good. Here, the lower hydrocarbon includes saturated hydrocarbons such as methane, ethane, propane and butane; unsaturated hydrocarbons such as ethylene, propylene, butylene, acetylene and butadiene; alcohols such as methanol, ethanol and isopropanol; acetone and acetylacetone Ketones such as: aldehydes such as formaldehyde and acetaldehyde.

In _SiN s _M t _O u _{C v} film of the gas barrier film 3, in the case of using the Mg in the M, _usually, since the magnesium oxide in the formation of the SiN _s M _t O u _{C v} film is deposited on the substrate 2, Of the manufacturing methods described above, it is preferable to use the ion plating method. By using the ion plating method, it becomes easy to deposit magnesium oxide (MgO) on the substrate 2. In addition, the ion plating method has an advantage of excellent productivity because the deposition rate (film formation rate) can be easily increased.

Furthermore, as a deposition method of SiN _s M _t O _u C _v film of the gas barrier film 3, using a vacuum deposition method, also preferred (the method using a method of performing beam heating by electron beam using an electron gun or less , Sometimes referred to as “electron gun physical vapor deposition”). In this case, when physical vapor deposition is performed, a predetermined gas such as a lower hydrocarbon may be flowed in the same manner as the reactive ion plating method described above. Further, when the gas barrier film 3 is formed, the lower the degree of vacuum, the easier it is to obtain high barrier performance.

(Transparent conductive film)
The transparent conductive film 4 is provided on the gas barrier film 3. More specifically, the transparent conductive film 4 is provided on the gas barrier film 3 in the gas barrier sheets 1B and 1C. Since the transparent conductive film 4 can be used as an anode of an organic EL display, the productivity of the organic EL display can be improved by providing the transparent conductive film 4.

  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 when such a forming method is used is, for example, indium-tin-based oxide (ITO), indium-tin-zinc-based oxide (ITZO), ZnO ₂ -based, CdO-based, and SnO ₂ -based. Etc. 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. 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 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)
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 surface of the substrate 2 opposite to the surface on which the gas barrier film 3 is formed. Thereby, since the gas barrier sheet 1C is protected by the hard coat film 5, as a result, it is possible 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. Examples of such materials include ethylene glycol di (meth) acrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, And bifunctional or higher acrylate monomers such as dipentaerythritol hexa (meth) acrylate. 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 sensitizers 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.

(Anchor coating film)
In the gas barrier sheet of the present invention, an anchor coating agent film 9 is preferably provided between the substrate 2 and the gas barrier film 3 as shown in FIG. The anchor coat agent film 9 reacts with a cardo polymer, a polyfunctional acrylic resin, a layered compound, a silane coupling agent having an organic functional group and a hydrolyzing group, and an organic functional group of the silane coupling agent. It is preferable to contain at least one of a composition composed of a crosslinkable compound having a second organic functional group and a raw material. According to this, the adhesiveness between the gas barrier film and the substrate can be improved, and as a result, a gas barrier sheet with high adhesiveness can be obtained.

  Examples of the cardo polymer used for the anchor coating agent film 9 include those having a side chain having an epoxy group, those having an acrylic group, and the like. Among these cardo polymers, those having an epoxy group are preferably used from the viewpoint of suppressing yellow coloring that occurs at high temperatures.

  Examples of the polyfunctional acrylic resin used for the anchor coating agent film 9 include 1,6-hexanediol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. And dipentaerythritol hexa (meth) acrylate and the like. Among these polyfunctional acrylic resins, it is preferable to use pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate from the viewpoint of low film stress and surface flatness.

  Examples of the layered compound used for the anchor coat agent film 9 include montmorillonite and layered silicate. Of these layered compounds, montmorillonite is preferably used from the viewpoint of productivity.

  Next, a silane coupling agent having an organic functional group and a hydrolyzable group used for the anchor coating agent film 9, and a crosslinkable compound having a second organic functional group that reacts with the organic functional group of the silane coupling agent. And a composition composed of these as raw materials.

  Examples of the organic functional group possessed by the silane coupling agent include γ-aminopropyltrimethoxy group, N-β (aminoethyl) γ-aminopropyltriisopropoxy group, and γ-aminopropyltriethoxy group. From the viewpoint of controlling reactivity, it is preferable to use a γ-aminopropyltrimethoxy group. Examples of the hydrolyzable group possessed by the silane coupling agent include a γ-glycidoxypropyl group, hexamethylene diisocyanate, and an oxazoline-containing polymer. The anchor coat agent film 9 has adhesion and flexibility. In view of the necessity of the property, it is preferable to use a γ-glycidoxypropyl group and an oxazoline-containing polymer. As such a silane coupling agent, preferably, γ-glycidoxypropyltrimethoxysilane can be mentioned.

  Examples of the second organic functional group that reacts with the organic functional group of the silane coupling agent in the crosslinkable compound include a methoxy group, an ethoxy group, and an isopropoxy group, and controls the reactivity. From the viewpoint, it is preferable to use a methoxy group or an isopropoxy group. Such crosslinkable compounds having a second organic functional group include polysiloxane compounds, such as tetramethoxysilane hydrolyzate, tetraethoxysilane hydrolyzate, hexamethylene disilazane hydrolyzate, and hexamethylene disiloxane hydrolyzate. It is preferable to use a tetraethoxysilane hydrolyzate from the viewpoint of reactivity control.

  The content of the crosslinkable compound relative to the silane coupling agent in the composition is usually 90% by weight or more and 99.99% by weight or less. Further, the composition may contain a predetermined amount of materials (raw materials) other than the silane coupling agent and the crosslinkable compound.

  The thickness of the anchor coating agent film 9 is usually 0.05 μm or more, preferably 0.1 μm or more, and 5 μm or less, preferably 1 μm or less. The formation of the anchor coating agent film 9 may be appropriately selected according to the material to be used, and a conventionally known method may be appropriately used.

(Other membranes)
In addition to the base material 2, the gas barrier film 3, the transparent conductive film 4, and the hard coat film 5 described above, other films can be used as necessary. As such, the anchor coating agent film 9 is as already described, but other examples include an antireflection film, an antistatic film, an antifouling film, an antiglare film, a color filter, and a smoothing film. it can. 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.

  As the smoothing film, a conventionally known film may be appropriately used. Examples of the material for the leveling 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 gas barrier film 3, the transparent conductive film 4, the hard coat film 5, the anchor coat agent film 9, and other films as necessary, the gas barrier sheets 1 </ b> A, 1 </ b> B, 1 </ b> C, 1D is formed. The gas barrier sheets 1A, 1B, 1C, and 1D have high productivity because the gas barrier film 3 has a predetermined composition, good gas barrier properties, curling is suppressed, and the adhesion of the gas barrier film 3 is improved. It will be expensive. In particular, even after a heat cycle test performed as a durability test for an organic EL display or the like, the occurrence of curling is suppressed and the gas barrier performance is also maintained.

The gas barrier sheets 1A, 1B, 1C, and 1D usually have 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 ·. It shows a high gas barrier property of atm (cc / m ² · day · atm) or less.

  When the gas barrier sheets 1A, 1B, 1C, and 1D are used as gas barrier sheets for light-emitting elements such as organic EL displays that require transparency, the gas barrier sheets 1A, 1B, 1C, and 1D are transparent. It is preferable. 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 sheets 1A, 1B, 1C, and 1D appear 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 sheets 1 </ b> A, 1 </ b> B, 1 </ b> C, 1 </ b> D, the occurrence of curling is suppressed by using a predetermined gas barrier film 3. FIG. 4 is a schematic cross-sectional view showing a method for measuring the degree of curling of the gas barrier sheet. First, the gas barrier sheets 1A, 1B, 1C, and 1D are cut into a predetermined size to prepare the 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, whereby the gas barrier sheets 1A, 1B, 1C, and 1D after the heat cycle test are measured. The curl degree can be evaluated. 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 a gas barrier sheet using a predetermined evaluation standard. The orthogonal distance L evaluated by such a method is usually controlled to be 1 mm or more and 3 mm or less before and after the heat cycle test. From the viewpoint of obtaining higher performance gas barrier sheets 1A, 1B, 1C, 1D, it is preferable to control the orthogonal distance L to be 1 mm or less.

  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. In addition, 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 such as an organic EL display. 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 glass or cans.

  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 _{1~7: SiN s M t O u} C v film, M = Mg)
A gas barrier sheet having a gas barrier film on a substrate was prepared by the film forming method and film forming conditions shown in Table-1. “IP” described in “Manufacturing method” in Table 1 indicates an ion plating method. In addition, a polyethylene naphthalate film (Teonex (registered trademark) Q65F, manufactured by Teijin DuPont Films Ltd.) having a thickness of 100 μm was used as the substrate.

  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)
The composition of the gas barrier film (values of s, t, u, and _v in SiN _s M _t O _u C _v ), more specifically, the atomic ratio of Si, N, M, O, and C is expressed as XPS (VG Measurement was carried out using ESCA LAB220i-XL (Scientific). As the X-ray source, MgKα ray which is an X-ray source having an Ag-3d-5 / 2 peak intensity of 300 Kcps to 1 Mcps was used, and a slit having a diameter of about 1 mm was used. The measurement was performed with the detector set on the normal line of the sample surface used for the measurement, and appropriate charge correction was performed. The analysis after the measurement uses the software Eclipse version 2.1 attached to the above-mentioned XPS apparatus, and binding of Si: 2p, N: 1s, Al: 2p, Mg: 2p, O: 1s, C: 1s The peak corresponding to the energy was used. 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. Shirley background was removed for each peak, and sensitivity coefficient correction for each element was made in the peak area (Si = 0.87, N = 1.77, Al = 0.67 for C = 1.0). , Mg = 0.36, O = 2.85), and the atomic ratio was determined. The carbon in this case was calculated excluding the peaks attributed to hydrocarbons. About the obtained atomic ratio, the number of Si atoms was set to 1, and the number of atoms of N, M, O, and C which are other components was calculated, and it was set as the component ratio. The obtained data is shown in the column of “Composition” in Table-2.

(Measurement of refractive index)
The refractive index of the gas barrier film was measured by UVISELTM manufactured by JOBIN YVON. The measurement was performed using a xenon lamp as a light source, an incident angle of −60 °, a detection angle of 60 °, and a measurement range of 1.5 eV to 5.0 eV. The obtained data is shown in the column of “refractive index” in Table-2.

(Measurement of gas barrier film thickness)
The thickness of the gas barrier film was measured using a step gauge (manufactured by ULVAC, Inc., DEKTAK IIA). The measurement was performed with the scan range set to 2 mm and the scan speed set to Low. The obtained data is shown in the column of “film thickness” in Table-2.

(Measurement of water vapor transmission rate)
The water vapor transmission rate was measured using a water vapor transmission rate measurement device (manufactured by MOCON, USA, PERMAT RAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. The obtained data is shown in the column “WVTR” of Table-2. The detection limit of the water vapor transmission rate measuring apparatus used for the measurement is 0.05 g / m ² · day, and when it is less than the detection limit, it is expressed as “ml (measuring 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. The obtained data is shown in the column “OTR” of Table-2. In addition, the detection limit of the oxygen gas permeability measuring apparatus used for the measurement is 0.05 cc / m ² · day · atm, and when it is less than the detection limit, it is expressed as “ml (measuring limit)”. Yes.

(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. The obtained data is shown in “immediately after film formation” in the “curl” column of Table-2.

○: 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 carried out by holding the gas barrier sheet sample 10 in an oven at 150 ° C. for 3 hours and then repeatedly cooling it 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. The obtained data is shown in “After heat resistance test” in the “Curl” column of Table-2.

(Adhesive evaluation)
Evaluation of adhesiveness (cross-cut method) was performed according to the description of 8.5.1 of JIS-K5400. Specifically, using a cutter guide with a gap interval of 2 mm, the cuts reaching the base material through the gas barrier film are made vertically and horizontally to form 100 grids, and cellophane adhesive tape (Nichiban 405 No. 24 mm width) ) Was attached to the square cut surface, rubbed with an eraser to completely adhere, and then peeled off vertically. The surface after peeling was visually observed, and the layer residual ratio in 100 squares (the part that was peeled off even if part of the squares was treated as the number of peeled) was taken as a measure of adhesiveness, and adhesiveness (%) = (1 -(Peeled squares / 100 squares)) x 100 was calculated and evaluated. The test by the cross-cut method was performed both immediately after the production of the gas barrier sheet and after the wet heat resistance test. The moisture and heat resistance test was performed by holding a gas barrier sheet for 100 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 (%) calculated by the above formula was 100% immediately after production and 100% after the wet heat resistance test in the gas barrier sheet of Example 1. In the gas barrier sheet of Example 2, it was 100% immediately after production and 100% after the wet heat resistance test. In the gas barrier sheet of Example 3, it was 100% immediately after production and 100% after the wet heat resistance test. In the gas barrier sheet of Example 4, it was 100% immediately after production and 100% after the moist heat resistance test. In the gas barrier sheet of Example 5, it was 100% immediately after production and 100% after the moist heat resistance test. In the gas barrier sheet of Example 6, it was 100% immediately after production and 100% after the wet heat resistance test. In the gas barrier sheet of Example 7, it was 100% immediately after production and 100% after the wet heat resistance test.

(Example _{8~11: SiN s M t O u} C v film, M = Al)
The gas barrier film in the same manner as _SiN s _M t _O u _{C v} film (M = Al) and was except that Examples 1 to 7 was prepared gas barrier sheet. The film forming method and film forming conditions are shown in Table-1. Moreover, the various characteristics of the obtained gas barrier sheet | seat were measured similarly to Examples 1-7. The results are shown in Table-2.

  Moreover, evaluation of the adhesiveness of the gas-barrier sheet | seat of each Example was performed like Example 1- Example 7. FIG. As a result, the adhesiveness (%) calculated by the above formula was 100% immediately after production and 100% after the wet heat resistance test in the gas barrier sheet of Example 8. In the gas barrier sheet of Example 9, it was 100% immediately after production and 100% after the wet heat resistance test. In the gas barrier sheet of Example 10, it was 100% immediately after production and 100% after the wet heat resistance test. In the gas barrier sheet of Example 11, it was 100% immediately after production and 100% after the wet heat resistance test.

(Comparative Example _{1~6: SiN s M t O u} C v film, M = Mg, Al)
The gas barrier film _SiN s _M t _O u _{C v} film (M = Mg, Al) and, except for changing the composition in the same manner as in Example 1 to Example 7, to produce a gas barrier sheet. Table 3 shows the film forming technique and film forming conditions. Moreover, the various characteristics of the obtained gas barrier sheet | seat were measured similarly to Examples 1-7. The results are shown in Table-4. In addition, “IP” described in “Manufacturing method” in Table 3 indicates an ion plating method, and “EB” indicates an electron gun type physical vapor deposition method. Comparative Examples 1 to 3 and 6 used Mg as M, and Comparative Examples 4 and 5 used Al as M. As shown in Table 4, the gas barrier sheet of Comparative Example 6 was colored.

(Example _{12~26: SiN s M t O u} C v film, M = Mg)
The gas barrier film as a _SiN s _M t _O u _{C v} film (M = Mg), except that changing the composition in the same manner as in Example 1 to Example 7, to produce a gas barrier sheet. Table-5 shows the film formation technique and film formation conditions. Moreover, the various characteristics of the obtained gas barrier sheet | seat were measured similarly to Examples 1-7. The results are shown in Table-6. In addition, “IP” described in “Manufacturing method” in Table-5 indicates an ion plating method, and “EB” indicates an electron gun type physical vapor deposition method.

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 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.

Explanation of symbols

1, 1A, 1B, 1C, 1D Gas barrier sheet 2 Base material 3, 3A, 3B Gas barrier film 4 Transparent conductive film 5 Hard coat film 6 Stainless steel substrate 8 Vertex 9 Anchor coat agent film 10 Gas barrier sheet sample

Claims (7)

In the gas barrier sheet having a gas barrier film on the substrate,
The gas barrier film is a SiNsMtOuCv film (where s = 0.5 to 1.5, t = 0.01 to 0.3, u = 0.25 to 1, v = 0 to 1, and M is Mg. .) A gas barrier sheet, wherein   The gas barrier sheet according to claim 1, wherein the v is 0, and the refractive index of the gas barrier film is 1.5 to 2.0.   The gas barrier sheet according to claim 1, wherein v is 0.1 to 1, and a refractive index of the gas barrier film is 1.8 to 2.2.   The gas barrier sheet according to any one of claims 1 to 3, wherein an extinction coefficient of the gas barrier film is 0.000001 or more and 0.03 or less.   The gas barrier sheet according to any one of claims 1 to 4, comprising a transparent conductive film on the gas barrier film.   The gas barrier sheet according to any one of claims 1 to 5, wherein a hard coat film is provided on at least one side of the gas barrier sheet.   An anchor coat agent film is provided between the base material and the gas barrier film, and the anchor coat agent film has a cardo polymer, a polyfunctional acrylic resin, a layered compound, and a silane cup having an organic functional group and a hydrolysis group. The composition according to any one of claims 1 to 6, comprising at least one of a composition composed of a ring agent and a crosslinkable compound having a second organic functional group that reacts with the organic functional group. The gas barrier sheet according to Item.

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