JP2017071133A - Gas barrier film laminate and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film laminate which is excellent in stability of a gas barrier layer against external pressure such as folding and which has high gas barrier property, and to provide an electronic device to which the gas barrier film laminate is applied, and which is excellent in durability.SOLUTION: A gas barrier film laminate GF has two units of gas barrier film units UA, UB respectively comprising a substrate 1A or 1B and a gas barrier layer 2A or 2B, in which the two gas barrier film units UA, UB are laminated via an adhesive layer 3, and 90° peel-back adhesive strength of the adhesive layer 3 measured at 23±1°C and under a condition of 50±5% of relative humidity based on JISZ0237:2009 is in the range of 3-20 N/25 mm for at least one of the gas barrier film units UA, UB.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film laminate and an electronic device, and more particularly, to a gas barrier film laminate having excellent stability against bending and the like and high gas barrier properties, and an electronic device using the same.

  Conventionally, in the fields of food, packaging materials, pharmaceuticals, etc., in order to prevent the permeation of gases such as water vapor and oxygen, it is relatively simple to provide an inorganic film such as a metal or metal oxide vapor deposition film on the surface of a resin support. Gas barrier films having a structure have been used.

  In recent years, such a gas barrier film that prevents permeation of water vapor, oxygen, and the like has been used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence elements (organic EL elements). It is being done. In order to give such an electronic device the property of being flexible and light and difficult to break, a gas barrier film having high gas barrier properties is required instead of a hard and easily broken glass substrate.

  As a method for obtaining a gas barrier film applicable to an electronic device, a gas barrier is formed on a resin support such as a film using a plasma CVD method (Chemical Vapor Deposition). A method of forming a layer and a method of forming a gas barrier layer by applying a surface treatment (modifying treatment) after applying a coating liquid containing polysilazane as a main component on a support (for example, patents) are known. See references 1 and 2.)

  Further, as a method for improving gas barrier properties, a transparent gas barrier laminated film in which two transparent gas barrier films are bonded together using an acrylic pressure-sensitive adhesive layer is disclosed (for example, see Patent Document 3). ). However, in Patent Document 3, there is no provision or disclosure regarding the adhesive strength of the pressure-sensitive adhesive layer to be applied, and there is no description regarding the relationship between the stress and the gas barrier property relating to the gas barrier layer when folded. Absent. In particular, there is no description about a method for preventing the occurrence of cracks in the gas barrier layer due to bending or the like received during manufacture or handling of the gas barrier film and achieving high gas barrier properties.

  On the other hand, a gas barrier film in which an antistatic layer is formed as a functional layer is disclosed (for example, see Patent Document 4). However, the method disclosed in Patent Document 4 aims to prevent fine foreign particles and the like from adhering to the gas barrier layer due to film charging when the gas barrier layer is formed in a vacuum environment. By bonding two gas barrier films through an adhesive layer to form a gas barrier film laminate, particularly by bending received during manufacture or handling of the gas barrier film A method for preventing the occurrence of cracks and the like in the gas barrier layer and achieving high gas barrier properties is not described.

JP 2009-255040 A JP 2012-148416 A Japanese Patent No. 4654911 JP 2006-88538 A

  This invention is made | formed in view of the said problem and the situation, The solution subject prescribes | regulates the adhesive force of an adhesive bond layer by the structure which bonded together two gas-barrier films through the adhesive layer. Thus, it is to provide a gas barrier film laminate having excellent gas barrier layer stability against an external pressure such as bending and having high gas barrier properties, and an electronic device having excellent durability to which the gas barrier film laminate is applied.

  In order to solve the above-mentioned problems, the present inventor, in the process of examining the cause of the above-mentioned problem, from the viewpoint of not concentrating stress on the gas barrier layer, an adhesive layer is provided between the two supports having the gas barrier layer. By providing and controlling the adhesive strength of the adhesive layer within a specific range, it is possible to provide a gas barrier film laminate having excellent gas barrier layer stability against external pressure such as bending and high gas barrier properties. I found it.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A gas barrier film laminate comprising at least two gas barrier film units each composed of a support and a gas barrier layer, each laminated via an adhesive layer,
The gas barrier film laminate according to claim 1, wherein the pressure-sensitive adhesive layer defined below has a pressure-sensitive adhesive force within a range of 3 to 20 N / 25 mm with respect to at least one of the gas barrier film units.

1. Adhesive strength: Adhesive strength peeled by 90 degrees measured in accordance with JIS Z 0237: 2009 under conditions of 23 ± 1 ° C. and relative humidity 50 ± 5%. The gas barrier film laminate according to item 1, wherein the pressure-sensitive adhesive layer has an adhesive strength in the range of 5 to 18 N / 25 mm.

  3. One surface side of the pressure-sensitive adhesive layer is in contact with a support constituting one gas barrier film unit, and the other surface side of the pressure-sensitive adhesive layer is in contact with a gas barrier layer constituting the other gas barrier film unit. 3. The gas barrier film laminate according to item 1 or 2, which has a constitution.

  4). The gas barrier film according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer is a pressure-sensitive pressure-sensitive adhesive layer and has a layer thickness in a range of 15 to 30 µm. Laminated body.

  5. The gas barrier film laminate according to any one of claims 1 to 4, wherein at least one of the gas barrier film units has an antistatic layer.

  6). The thickness of the at least 1 support body which comprises the said gas-barrier film unit exists in the range of 20-50 micrometers, The gas barrier as described in any one of Claim 1-5 characterized by the above-mentioned. Film laminate.

  7). An electronic device comprising the gas barrier film laminate according to any one of items 1 to 6.

  By defining the adhesive strength of the adhesive layer by the above means of the present invention, the gas barrier film laminate having excellent gas barrier layer stability against external pressure during bending (also referred to as bending) and having high gas barrier properties. And the electronic device excellent in durability which applied it can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  In general, it is known that a structure in which a gas barrier layer is provided on both sides of a support is effective in developing a high gas barrier property in a gas barrier film. However, in the configuration in which the gas barrier layer is simply provided on the support, when a stress such as bending is applied from the outside, the stress cannot be dispersed by a single support, and the strain (stress) is caused by the gas barrier. Since it extends to the layers, cracks due to the film surface rupture of the gas barrier layer and the like occur, causing a reduction in gas barrier properties.

  In the gas barrier film laminate of the present invention, two gases having a gas barrier layer formed on a support are bonded to each other via an adhesive layer. The characteristics of the pressure-sensitive adhesive layer sandwiched between the barrier films, specifically the adhesiveness, is important for relaxing the stress applied and developing gas barrier properties having high stability.

  That is, the structure in which the support having two gas barrier layers is bonded to both surfaces via the pressure-sensitive adhesive layer is to connect the spaced-apart support to one via the pressure-sensitive adhesive layer. In order to prevent stress from concentrating on the gas barrier layer formed on the two bonded substrates, the role of the pressure-sensitive adhesive layer formed between them is very important.

  In a conventional structure in which a gas barrier layer is provided on a support, when the gas barrier layer is formed on the support by a roll-to-roll method, or after film formation, the gas barrier film is conveyed or wound. In the subsequent work, the formed gas barrier layer is likely to be subjected to a large stress. Further, if the support itself is a thin film, the stress on the gas barrier layer is increased, and as a result, cracks occur in the gas barrier layer. In addition, when the adhesion of the gas barrier layer to the support deteriorates, a desired gas barrier property cannot be obtained.

  In particular, from the viewpoint of meeting the demand for high-quality gas barrier properties, the gas barrier film having a plurality of gas barrier layers has a plurality of gas barrier layers. Due to stress at the layer interface, stress propagates to multiple layers, cracks occur, the effect of stacking multiple layers is significantly impaired, and as a result, it has a major problem of causing a decrease in gas barrier properties. Improvement was desired.

  In the gas barrier film laminate of the present invention, by providing an adhesive layer between a support having two gas barrier layers that are separated from each other, the adhesive layer exhibits a stress relaxation function, It has been found that the stress relaxation ability can provide a stable gas barrier property without giving excessive stress to the gas barrier layer by defining the adhesive force of the adhesive layer to the support.

  If the adhesive force imparted to the pressure-sensitive adhesive layer is too lower than the conditions specified in the present invention, the gas barrier is formed when subjected to bending on a transport roll or bending during handling during film formation on a roll-to-roll. Between the adhesive film and the adhesive layer, fine voids are likely to occur, which causes uneven stress on the gas barrier layer, causing local stress and causing cracks in the thin gas barrier layer. It becomes easy.

  On the other hand, if the adhesive strength is too high, the gas barrier film and the pressure-sensitive adhesive layer will adhere strongly, but it will be applied when bending on the transport roll during roll-to-roll film formation or bending during handling. It becomes difficult to express the ability to relieve stress in the pressure-sensitive adhesive layer, and stress concentrates on the gas barrier layer, which is the least resistant of the thin film. As a result, cracks are generated in the gas barrier layer, and the gas barrier property is greatly deteriorated. It has been found.

  That is, from the viewpoint of not concentrating stress on the gas barrier layer, the adhesive force of the pressure-sensitive adhesive layer provided between the supports having the two gas barrier layers is set within a specific range where stress can be relaxed. The present invention has been found to be important for realizing a gas barrier film laminate having excellent coating film stability with respect to external pressure such as high gas barrier properties.

Schematic sectional view showing an example of the overall configuration of the gas barrier film laminate of the present invention Schematic sectional drawing which shows an example of the whole structure of the electronic device which comprised the gas barrier film laminated body of this invention Schematic sectional view showing another example of the overall configuration of the gas barrier film laminate of the present invention Schematic sectional view showing an example of a plasma CVD apparatus applicable to the formation of a gas barrier layer according to the present invention Schematic sectional view showing an example of a vacuum ultraviolet light irradiation apparatus applicable to the formation of a gas barrier layer according to the present invention

  The gas barrier film laminate of the present invention is a gas barrier film laminate in which two gas barrier film units each composed of at least a support and a gas barrier layer are laminated via an adhesive layer. In accordance with JIS Z 0237: 2009 of the pressure-sensitive adhesive layer for at least one of the gas barrier film units, the 90 ° peel-off adhesive strength measured under the conditions of 23 ± 1 ° C. and relative humidity 50 ± 5% 3 to 20 N / 25 mm. This feature is a technical feature common to the inventions according to claims 1 to 7.

  As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, it is further possible to set the adhesive strength of the pressure-sensitive adhesive layer within a range of 5 to 18 N / 25 mm, which is a gas barrier against external pressure for better bending and the like. This is preferable in that the stability of the layer can be obtained.

  Further, one surface side of the pressure-sensitive adhesive layer is in contact with a support constituting one gas barrier film unit, and the other surface side of the pressure-sensitive adhesive layer is a gas barrier layer constituting the other gas barrier film unit. In the electronic device to which this is applied, it is preferable that the structure is in contact with the organic device from the viewpoint of exhibiting excellent gas barrier properties with respect to the organic functional layer and the like, and improving resistance to scratches and the like.

  In addition, the pressure-sensitive adhesive layer as the pressure-sensitive adhesive layer and the layer thickness within the range of 15 to 30 μm can stably realize the range of 90-degree peeling adhesive force defined in the present invention. And it is preferable from the viewpoint that an effective stress relaxation ability can be expressed.

  Further, it is preferable that at least one of the gas barrier film units has an antistatic layer when the gas barrier layer is formed, in the environment of the film forming apparatus or on the surface of the transport roller in the transport process. It is preferable in that the fine particles can be prevented from adhering due to film charging when forming the gas barrier layer, and the occurrence of defects in the gas barrier layer due to foreign matters can be prevented.

  Further, the thickness of at least one support constituting the gas barrier film unit can be within a range of 20 to 50 μm, so that a thin gas barrier film laminate can be formed, which is suitable for a thin electronic device. It is preferable in that it can be used.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit. In the description of each figure, numerals and the like described in parentheses after the constituent elements indicate the reference numerals described in each figure.

<Gas barrier film laminate>
[Basic structure of gas barrier film laminate and electronic device]
The gas barrier film laminate of the present invention has two units of a gas barrier film unit composed of a support and a gas barrier layer, and the adhesive layer is sandwiched between the two gas barrier film units. A laminated gas barrier film laminate, wherein the pressure-sensitive adhesive layer conforms to JIS Z 0237: 2009 for at least one of the gas barrier film units and has a relative humidity of 23 ± 1 ° C. and a relative humidity of 50 ± 5%. The 90 degree peeling adhesive strength measured under conditions is in the range of 3 to 20 N / 25 mm.

  A specific configuration of the gas barrier film laminate of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of the overall structure of the gas barrier film laminate of the present invention.

  The gas barrier film laminate (GF) shown in FIG. 1 has a first gas barrier layer A (on the support A (1A) on one surface side of the pressure-sensitive adhesive layer (3) via the interface A. 2A) having a gas barrier film unit A (UA), and on the other surface side of the pressure-sensitive adhesive layer (3), the second gas barrier is provided on the support B (1B) via the interface B. The gas barrier film unit B (UB) having the layer B (2B) is arranged.

  In the present invention, at least one of the interface A and the interface B, the 90-degree peeling adhesive strength is in the range of 3 to 20 N / 25 mm.

  As a structure of the gas barrier film unit arrange | positioned on both surfaces of an adhesive layer (3), if the adhesive force prescribed | regulated by this invention is satisfy | filled, there will be no restriction | limiting, As shown in FIG. In the interface A, the pressure-sensitive adhesive layer (3) and the support A (1A) constituting the gas barrier film unit A (UA) are arranged, and the first gas barrier layer A (2A) is provided on the outermost surface. And in the other interface B, it has the adhesive layer (3) and the second gas barrier layer B (2B) constituting the gas barrier film unit B (UB), and the support B on the outermost surface. A configuration in which (1B) is arranged is a preferred embodiment.

  When the gas barrier film laminate (GF) having the configuration shown in FIG. 1 is applied to an electronic device, for example, an organic EL element as shown in FIG. 2 described later, an organic EL that is easily affected by oxygen, moisture, or the like. From the viewpoint of efficiently protecting the organic functional layer including the light emitting layer constituting the element, it is effective to dispose the first gas barrier layer A (2A) at the interface with the organic EL element. It is.

  As shown in (a) of FIG. 3 to be described later, the support A (1A) can be disposed on the outermost surface side. However, when such a configuration is applied to an organic EL element or the like, a support is provided. In some cases, the body A (1A) itself contains moisture or the like, and when the influence of the moisture on the organic functional layer is taken into consideration, the configuration shown in FIG. 1 is preferable.

  On the other hand, as shown in FIG. 1, as the configuration of the gas barrier film unit B (UB) on the other surface side, the support B (1B) is disposed on the outermost surface, which prevents scratches during handling. It is preferable from the viewpoint.

  FIG. 2 is a schematic cross-sectional view showing an example of the overall configuration of an electronic device including the gas barrier film laminate having the configuration illustrated in FIG.

  In FIG. 2, on the gas barrier film laminate (GF) having the structure shown in FIG. 1, the first carrier transporting functional layer (5) mainly controlling the transport of the anode (4), electrons or holes. ), A light emitting layer (6), a second carrier transporting functional layer (7) for controlling electron or hole transport, a cathode (8), a sealing adhesive layer (9), and a sealing substrate (10). The electronic device (D) is formed by stacking the organic EL elements (EL).

  In the electronic device (D) having such a configuration, a gas barrier film unit A (UA) is formed at the interface contacting the gas barrier film laminate (GF) and the organic EL element (EL). The gas barrier layer A (2A) is disposed in the first carrier transporting functional layer (5), the light emitting layer (6), and the electron or hole transport composed of the organic material on the upper side. This is a preferable configuration in that effective gas barrier properties for the second carrier transporting functional layer (7) to be controlled can be expressed. In addition, as described above, the support B (1B) of the gas barrier film unit B (UB) is preferably disposed on the back side of the electronic device (D) from the viewpoint of scratch resistance and the like. .

  Moreover, in the gas barrier film laminated body of this invention, in addition to the structure shown in FIG. 1, various layer structure can be taken as needed.

  FIG. 3 is a schematic cross-sectional view showing another example of the overall configuration of the gas barrier film laminate of the present invention.

  The gas barrier film laminate (GF) shown in (a) of FIG. 3 includes gas barrier layers (2A, 2B) constituting the gas barrier film unit A (UA) and the gas barrier film unit B (UB). ) Shows a configuration example in contact with the pressure-sensitive adhesive layer (3). The gas barrier film laminate (GF) having such a configuration is an effective configuration when used as a gas barrier film alone.

  The gas barrier film laminate (GF) shown in FIG. 3B is a support (1A, 2A) constituting the gas barrier film unit A (UA) and the gas barrier film unit B (UB). Shows a configuration example in contact with the pressure-sensitive adhesive layer (3). The gas barrier film laminate (GF) having such a configuration is effective in a configuration in which organic EL elements and the like are arranged on both surfaces of the laminate.

[Measurement method of adhesive strength]
In the present invention, the pressure-sensitive adhesive layer according to the present invention is characterized in that the adhesive strength with respect to at least one of the gas barrier film units is in the range of 3 to 20 N / 25 mm, more preferably 5 Within the range of ~ 18N / 25mm.

  The adhesive strength defined in the present invention refers to a 90-degree peeling adhesive strength measured in accordance with JIS Z 0237: 2009, with a sample width of 25 mm, measured at 23 ± 1 ° C. and relative humidity of 50 ± 5%.

  As a test apparatus used for the measurement, a tensile test apparatus is used, and a tensile tester specified in JIS B 7721 or a tensile tester equivalent thereto is used. The capacity of the measuring device is such that the measured value falls within the range of 15 to 85% of the capacity. The tensile speed is 5 ± 0.2 mm / s, and the reading tolerance is 2% or less. As a method for displaying the measured value, an analog type, a digital type, or the like can be used.

  In the present invention, in the measurement of the peel adhesive force described in the adhesive tape / adhesive sheet test method of JIS Z 0237: 2009, the measurement was performed under the following conditions in accordance with the 90-degree adhesive force test method. Went.

  -Measuring apparatus: A tensile tester combined with the following apparatus manufactured by Imada Co., Ltd. was used.

Gauge; ZP-50N
Slad table; P90-200N
Stand; MX2-500N
Measurement environment: 23 ± 1 ° C, relative humidity 50 ± 5%
<Constituent elements of gas barrier film laminate>
The gas barrier film laminate of the present invention has at least two gas barrier film units each composed of a support and a gas barrier layer, and the adhesive layer is sandwiched between the two gas barrier film units. It is a configuration.

[Adhesive layer]
The pressure-sensitive adhesive layer according to the present invention is a 90-degree peeling film measured at 23 ± 1 ° C. and a relative humidity of 50 ± 5% in accordance with JIS Z 0237: 2009 for at least one gas barrier film unit. The adhesive strength is in the range of 3 to 20 N / 25 mm, and more preferably in the range of 5 to 18 N / 25 mm.

  When the adhesive strength of the pressure-sensitive adhesive layer defined in the present invention is less than 3 N / 25 mm, for example, in the production process of a roll-to-roll system of a gas barrier film laminate, bending or handling on a transport roll When subjected to bending at times, fine gaps are likely to occur between the gas barrier film and the adhesive layer, which causes uneven stress on the gas barrier layer, resulting in local stress. The thin gas barrier layer is likely to crack.

  On the other hand, when the adhesive strength of the pressure-sensitive adhesive layer specified in the present invention exceeds 20 N / 25 mm, the pressure-sensitive adhesive strength becomes excessively high, and the gas barrier film and the pressure-sensitive adhesive layer adhere firmly, but roll-to- It is difficult to express in the adhesive layer the ability to relieve the stress when bending on the transport roll or bending during handling in the roll manufacturing process. Stress concentrates on the barrier layer, and as a result, cracks are generated in the gas barrier layer, causing a significant deterioration in gas barrier properties.

  The pressure-sensitive adhesive layer according to the present invention is not particularly limited as long as the constituent material can obtain the adhesive strength defined in the present invention, but the pressure-sensitive adhesive layer is preferably a pressure-sensitive pressure-sensitive adhesive layer. is there.

  The material constituting the pressure-sensitive adhesive layer for bonding the two gas barrier film units according to the present invention is not a curable adhesive that can be cured by thermosetting resin or UV irradiation to obtain an adhesive force, It is preferable to apply a pressure sensitive adhesive.

  This pressure-sensitive adhesive has cohesive strength and elasticity, can maintain stable adhesiveness for a long time, and does not require requirements such as heat or organic solvent when forming an adhesive layer, only a slight pressure By utilizing the anchoring effect, the two gas barrier film units can be stably bonded.

  The cohesive force here is equivalent to the force that the adhesive can withstand internal destruction, and the elasticity is applied again when an object that has undergone a change in shape or volume due to external force is removed. It corresponds to the property of recovering to the state.

  Due to the cohesive force and elasticity of the pressure-sensitive adhesive suitable for the present invention, when the gas barrier film laminate itself is subjected to external stress, the gas barrier film laminate Therefore, it is possible to prevent the gas barrier layer from being damaged.

  As a material constituting the pressure-sensitive adhesive layer according to the present invention, a material having excellent transparency is used. Examples of the constituents of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic resins, rubber resins, urethane resins, vinyl ether resins, silicon resins, and the like. There are molds and hot melt molds.

  In addition to the above-mentioned resins constituting the pressure-sensitive adhesive, various additives, for example, natural resins such as rosin, modified rosin, rosin and modified rosin derivatives, polyterpene resins, from the viewpoint of improving the physical properties of the pressure-sensitive adhesive layer, Modified terpene, aliphatic hydrocarbon resin, cyclopentadiene resin, aromatic petroleum resin, phenol resin, alkyl-phenol-acetylene resin, coumarone-indene resin, vinyltoluene-α-methylstyrene copolymer And other tackifiers, anti-aging agents, stabilizers, and softeners can be added as necessary. These may be used in combination of two or more as required. Moreover, in order to improve light resistance, organic ultraviolet absorbers, such as a benzophenone series or a benzotriazole series, can be added to an adhesive.

  As a method of forming the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive to the support surface constituting any of the gas barrier film units to be laminated and drying it as necessary.

  As a device for applying the adhesive to the support, a reverse roll coater, knife coater, bar coater, slot die coater, air knife coater, reverse gravure coater, vario gravure coater, or the like is used. If the coating amount of the pressure-sensitive adhesive is too thick, the amount of water retained in the high-humidity environment of the pressure-sensitive adhesive itself will increase, which will adversely affect the gas barrier properties of the gas barrier layer. Therefore, the thickness of the pressure-sensitive adhesive layer is preferably in the range of 10 to 50 μm, more preferably in the range of 10 to 40 μm, and particularly preferably in the range of 15 to 30 μm.

  Alternatively, an adhesive film may be used with an adhesive layer sandwiched between two upper and lower separator films. In this case, it can be bonded to the gas barrier film unit using tension and pressure as parameters.

  The pressurizing pressure is not particularly limited as long as the desired adhesive force can be obtained, but is preferably in the range of 5 to 600 kPa, more preferably 10 to 500 kPa. Heating may be performed as needed without any particular limitation, but it is preferable to set the temperature within the range from room temperature to Tg of the support constituting the gas barrier film unit.

[Gas barrier film unit]
The gas barrier film laminate of the present invention is characterized in that two gas barrier film units composed of at least a support and a gas barrier layer are disposed on both sides of the pressure-sensitive adhesive layer. .

  The gas barrier film unit according to the present invention may be any structure as long as it has at least one gas barrier layer on the support, but the gas barrier layer is a laminate of two or more layers. It may be. In the present invention, the gas barrier layer is composed of a plurality of gas barrier layers, and the plurality of gas barrier layers are formed by irradiating a composition containing a polysilazane compound with vacuum ultraviolet light (hereinafter also referred to as VUV light). It is preferable that the gas barrier layer and the gas barrier layer formed by vapor deposition have at least one layer each.

[Support]
As a support constituting the gas barrier film unit according to the present invention (hereinafter also referred to as a support), as long as it can hold the gas barrier layer (2A, 2B) having gas barrier properties, It is not particularly limited.

  Examples of the support applicable to the present invention include acrylic ester, methacrylic ester, polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (abbreviation: PEN), polycarbonate (abbreviation: PC), poly Arylate, polyvinyl chloride (abbreviation: PVC), polyethylene (abbreviation: PE), polypropylene (abbreviation: PP), polystyrene (abbreviation: PS), nylon (abbreviation: Ny), aromatic polyamide, polyether ether ketone, polysulfone, Heat-resistant transparent film based on a film composed of resins such as polyethersulfone, polyimide, polyetherimide, cycloolefin polymer, cycloolefin copolymer, etc., and a silsesquioxane having an organic-inorganic hybrid structure. Beam (product name Sila-DEC, manufactured by Chisso Corporation), and further can be mentioned hybrid resin film formed by laminating the resin two or more layers.

  From the viewpoint of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN) and the like are preferably used. From the viewpoint of low retardation, cycloolefin polymer, cycloolefin copolymer and polycarbonate (PC). Are preferably used. Further, in terms of optical light transmittance, heat resistance, and adhesion to the gas barrier layer, a heat resistant transparent film having a silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton can be preferably used. In addition, it is also preferable to use polyimide or the like as the heat-resistant support. This is because a heat-resistant support (for example, Tg> 200 ° C.) can be used for heat treatment at a temperature of 200 ° C. or higher in the manufacturing process of the electronic device. The resistance of the transparent conductive layer necessary for improving the driving efficiency of the device or the pattern layer made of metal nanoparticles can be reduced, and as a result, the initial characteristics of the electronic device can be greatly improved. Further, the thickness of the support is preferably about 5 to 500 μm, more preferably 15 to 250 μm, and particularly preferably a gas barrier film unit from the viewpoint of obtaining a thin gas barrier film laminate. It is preferable that the thickness of at least one support that constitutes is in the range of 20 to 50 μm.

  Moreover, it is preferable that the support body which concerns on this invention is transparent, ie, has a light transmittance. Since the support is light-transmitting and the constituent layer formed on the support is also light-transmitting, it is possible to obtain a gas barrier film laminate having light-transmitting properties. This is because it can be applied as a transparent substrate such as an EL element.

  The term “light transmittance” or “transparent” as used in the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more, preferably 60% or more, more preferably 70% or more, and particularly preferably 80%. That's it.

  Further, the support using the above-described resin material or the like may be an unstretched film or a stretched film.

  The support used in the present invention can be produced by a conventionally known general method. For example, a melt casting method for producing an unstretched substrate that is substantially amorphous and not oriented by melting a resin as a material by an extruder, extruding it by an annular die or a T die, and quenching, After preparing a dope prepared by dissolving a resin as a material in an organic solvent or the like, a solution casting method in which the dope is cast into an endless metal belt and dried to produce an unstretched support can be applied. it can.

  In addition, the unstretched support may be transported in the support direction (vertical axis, MD) by a known method such as uniaxial stretching, tenter sequential biaxial stretching, tenter simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like. A stretched support can be produced by stretching in a direction (lateral direction, TD direction) perpendicular to the conveyance direction of the support (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably in the range of 1.05 to 10 times in the vertical axis direction and the horizontal axis direction.

  Further, in the support according to the present invention, on the side where the gas barrier layer according to the present invention is provided, various known treatments for improving adhesion, for example, corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment. Alternatively, lamination of a smooth layer, which will be described later, may be performed, or the above processes may be combined.

[Formation of gas barrier layer]
As a method for forming a gas barrier layer according to the present invention, a vapor deposition method typified by a reactive vapor deposition method, a sputtering method, a chemical vapor volume method (CVD method), a polysilazane is irradiated with vacuum ultraviolet light, and silicon oxide or There is a wet vacuum ultraviolet light modification method in which a gas barrier layer is formed by modification to silicon oxynitride.

(Formation of gas barrier layer by vapor deposition)
<Reactive vapor deposition method>
Reactive vapor deposition is a method in which reactive gas is introduced into a vacuum vessel and atoms and molecules evaporated from the evaporation source are reacted and deposited. In order to accelerate the reaction, an excitation source such as plasma is introduced. You can also. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride, or the like is used as a deposition source, and nitrogen, hydrogen, ammonia, oxygen, or the like is used as a reactive gas.

<Sputtering method>
The sputtering method is a method of depositing constituent atoms of a sputtered target on a support using a sputtering phenomenon in which high-energy ions accelerated by an electric field are incident on a target and the constituent atoms of the target are knocked out. The reactive sputtering method is a method in which a reactive gas is introduced into a vacuum vessel, reacted with constituent atoms of a sputtered target, and deposited on a support. As typical raw materials, silicon, silicon nitride, silicon oxide, silicon oxynitride or the like is used as a target material, and nitrogen, hydrogen, ammonia, oxygen or the like is used as a reactive gas.

<Chemical vapor deposition method>
In the chemical vapor deposition method, a material gas containing a constituent element of a film is introduced into a vacuum vessel, and the material gas is excited by a specific excitation source, thereby forming an excited species by a chemical reaction and depositing it on a support. Is the method. As typical raw materials, monosilane, hexamethyldisilazane, tetraethoxysilane, ammonia, nitrogen, hydrogen, oxygen and the like are used.

  The chemical vapor deposition method is an effective gas barrier layer forming method because it can form a film at a high speed and has better coverage on the support than the sputtering method or the like. In particular, a catalytic chemical vapor deposition (Cat-CVD) method using a very high temperature catalyst as an excitation source and a plasma chemical vapor deposition (plasma CVD) method using plasma as an excitation source are preferable methods. Hereinafter, these methods will be described in detail.

<Cat-CVD method>
Cat-CVD is a method in which a material gas is allowed to flow into a vacuum vessel in which a wire made of tungsten or the like is arranged, and a material gas is contacted and decomposed by a wire heated by a power source to support the generated reactive species. It is a method of depositing on the body.

For example, when depositing silicon nitride, monosilane, ammonia, or hydrogen is used as the material gas. In the case of depositing silicon oxynitride, oxygen is added in addition to the above material gas. As a condition example, a tungsten wire (eg, φ0.5, length 2.8 m) as a catalyst body is heated to 1800 ° C., and monosilane, ammonia, and hydrogen (4/200/200 sccm) are distributed as material gases. Then, the pressure is maintained at 10 Pa, and a film is deposited on the support adjusted to 100 ° C. Of the reactive species generated by the decomposition reaction on the catalyst body, the main deposition species are SiH ₃ ^* and NH ₂ ^* , and H ^* is a reaction auxiliary species on the film surface. In particular, by adding hydrogen, a large amount of H ^* can be generated and the deposition rate is reduced, but it is considered that the reaction for removing H derived from Si—H bonds and N—H bonds in the film is promoted. .

<Plasma CVD method>
In the plasma CVD method, a material gas is introduced into a vacuum vessel equipped with a plasma source, and power is supplied from the power source to the plasma source, thereby generating discharge plasma in the vacuum vessel and causing the material gas to decompose and react with the plasma. A reactive species deposited on a support. As a plasma source system, a capacitively coupled plasma using parallel plate electrodes, an inductively coupled plasma, a microwave excitation plasma using a surface wave, a plasma CVD apparatus using a roll power source, or the like is used.

  FIG. 4 is a schematic view showing an example of a discharge plasma CVD apparatus having a pair of rollers to which a magnetic field that can be suitably used in the production of the gas barrier film laminate of the present invention is applied.

  The inter-roller discharge plasma CVD apparatus (31, hereinafter also referred to as plasma CVD apparatus) to which a magnetic field shown in FIG. 4 is applied mainly includes a delivery roller (32) and a transport roller (33, 34, 35, and 36). A film forming roller (39 and 40), a film forming gas supply pipe (41), a plasma generation power source (42), and a magnetic field generator (43 installed in the film forming roller (39 and 40)). And 44) and a winding roller (45). In such a plasma CVD apparatus (31), at least the film forming rollers (39 and 40), the film forming gas supply pipe (41), the plasma generating power source (42), and the magnetic field generating apparatus (43 and 40) are provided. 44) are arranged in a vacuum chamber (C). Furthermore, in such a plasma CVD apparatus (31), the chamber (C) is connected to a vacuum pump (17), and the pressure in the chamber (C) can be adjusted appropriately by this vacuum pump (17). It is possible.

  In such a plasma CVD apparatus, each film-forming roller is for plasma generation so that a pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. Connected to the power supply (42). By supplying electric power to the pair of film forming rollers (the film forming roller 39 and the film forming roller 40) from the power source (42) for generating plasma, the film forming roller (39) and the film forming roller (40) are separated from each other. It is possible to discharge into a space, and thus plasma can be generated in a space (also referred to as a discharge space) between the film formation roller (39) and the film formation roller (40). In addition, since the film-forming roller (39) and the film-forming roller (40) are used as electrodes in this way, the materials and designs that can be used as electrodes may be changed as appropriate. Moreover, in such a plasma CVD apparatus (31), it is preferable that the pair of film forming rollers (film forming rollers 39 and 40) are arranged so that their central axes are substantially parallel on the same plane. In this way, the film forming rate can be doubled by arranging the pair of film forming rollers (film forming rollers 39 and 40).

  Further, inside the film forming roller (39) and the film forming roller (40), magnetic field generators (43 and 44) fixed so as not to rotate even when the film forming roller rotates are provided, respectively. .

<1> Raw Material Gas In the formation of the gas barrier layer according to the present invention by plasma CVD, it is preferable to use an organosilicon compound containing at least silicon as the raw material gas constituting the gas used for film formation.

  Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethyl. Examples thereof include silane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  The film-forming gas contains oxygen gas as a reaction gas in addition to the source gas. The oxygen gas is a gas that reacts with the raw material gas to become an inorganic compound such as an oxide.

  As the film forming gas, a carrier gas may be used as needed to supply the source gas into the chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

<2> Degree of vacuum The pressure (degree of vacuum) in the chamber (C) can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 100 Pa.

[Formation of gas barrier layer by modifying polysilazane]
As a gas barrier layer according to the present invention, a coating liquid for forming a polysilazane layer containing polysilazane is applied and dried to form a precursor layer. Then, the polysilazane-containing layer is subjected to a modification treatment with vacuum ultraviolet light to form a gas barrier. A method of forming a layer (hereinafter also referred to as a vacuum ultraviolet light modification method) can be preferably used.

  The polysilazane modification treatment in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.

  For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. The formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate using a resin film as the support 1. Therefore, when producing the gas barrier film of the present invention, a conversion reaction using ultraviolet light capable of a conversion reaction at a lower temperature is preferable from the viewpoint of adaptation to a plastic substrate.

  In the method for producing a gas barrier film in the present invention, the polysilazane coating film from which moisture has been removed is modified by treatment with ultraviolet light irradiation. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.

This ultraviolet light irradiation excites and activates O ₂ and H ₂ O, UV absorbers, and polysilazane itself that contribute to ceramicization. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.

  Any commonly used ultraviolet ray generator can be used for the vacuum ultraviolet ray irradiation treatment in the present invention. The ultraviolet light referred to in the present invention generally refers to ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm called vacuum ultraviolet light.

  For the irradiation with vacuum ultraviolet light, it is preferable to set the irradiation intensity and the irradiation time within a range in which the support 1 carrying the polysilazane layer before the modification to be irradiated is not damaged.

Taking the case of using a plastic film as a support, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the support surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the support and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation for 0.1 second to 10 minutes can be performed.

  In general, when the temperature of the support during the ultraviolet irradiation treatment is 150 ° C. or higher, the characteristics of the support are impaired in the case of a plastic film or the like, for example, the support is deformed or its strength is deteriorated. . However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the support temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of support. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the support used. When the support 1 having a polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in a drying zone having the ultraviolet ray generation source as described above while being conveyed. be able to. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the support used and the polysilazane modified layer.

  Moreover, it is preferable to make oxygen concentration into 300-10000 ppm (1%) at the time of irradiating a vacuum ultraviolet light (VUV), More preferably, it is 500-5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of an oxygen-excess gas barrier layer and to prevent deterioration of the barrier property.

  A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.

  The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  Specifically, the modification treatment method for the polysilazane layer before modification in the present invention is treatment by irradiation with vacuum ultraviolet light. The treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is called a photon process called a photon process. This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

In the vacuum ultraviolet light irradiation step of the present invention, the illuminance of the vacuum ultraviolet light in the coating film surface for receiving the polysilazane coating film is more preferably 30~200mW / cm ^2, is 50~160mW / cm ² And more preferred. If it is 30 mW / cm ² or more, the reforming efficiency can be sufficiently exhibited, and if it is 200 mW / cm ² or less, problems such as ablation of the coating film or damage to the support are prevented. be able to.

Irradiation energy amount of the vacuum ultraviolet light in the polysilazane coating film surface is preferably 10~30000mJ / cm ^2, more preferable to be 100~15000mJ / cm ^2, further preferably a 200~12000mJ / cm ^2. If 10 mJ / cm ² or more is sufficient as the modification effect can if 30000mJ / cm ² or less, to suppress the occurrence of thermal deformation of cracks or support.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by placing a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar discharge called micro discharge.

  As a method for efficiently obtaining excimer light emission, electrodeless field discharge is also known in addition to dielectric barrier discharge. The electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge. The lamp and electrodes and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. In the electrodeless field discharge, a spatially and temporally uniform discharge can be obtained in this way.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are irradiated. It is possible.

  In addition, since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for irradiation to a gas barrier film using a resin film such as polyethylene terephthalate which is considered to be easily affected by heat as a support.

  In the present invention, the gas barrier layer is formed by applying a gas barrier layer forming coating solution containing a polysilazane compound.

  As a coating method, any appropriate wet coating method can be applied. For example, a roller coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and the like. Examples thereof include a coating method and a gravure printing method.

  The thickness of the coating film can be set according to the purpose of use of the gas barrier film and is not particularly limited. For example, the thickness of the coating film is preferably 0.01 to 1 μm as the thickness after drying. More preferably, it is in the range of 20 to 600 nm, and most preferably in the range of 40 to 400 nm.

The “polysilazane compound” preferably used in the present invention is a polymer having a silicon-nitrogen bond in the structure, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N _4, and an intermediate between them. It is a ceramic precursor inorganic polymer such as solid solution SiO _x N _y .

In order to apply the film without damaging the film support, a polysilazane compound that is modified to SiO _x N _y at a relatively low temperature is preferable, as described in JP-A-8-112879.

  As such a polysilazane compound, those having the following structure are preferably used.

—Si (R ₁ ) (R ₂ ) —N (R ₃ ) —
In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

In the present invention, from the viewpoint of the denseness of the resulting gas barrier layer as a film, perhydropolysilazane (abbreviation: PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms is particularly preferable.

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to the base support is improved and the polysilazane which is hard and brittle Thus, there is an advantage that the generation of cracks can be suppressed even when the film thickness is increased.

  These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6-membered ring or an 8-membered ring coexist.

  The molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight.

  These polysilazanes are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be used as they are as a polysilazane-containing coating solution.

  Other examples of the polysilazane compound that is ceramicized at a low temperature include a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), and a glycidol-added polysilazane obtained by reacting glycidol ( JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-6240) 299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (JP-A-7) -19 986 JP), and the like.

  As an organic solvent for preparing a coating solution containing a polysilazane compound, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane.

  Examples of the organic solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, and ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers.

  Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran.

  These organic solvents may be selected according to the purpose, such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed.

  The concentration of the polysilazane compound in the polysilazane compound-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the film thickness of the target second gas barrier layer and the pot life of the coating solution.

  An amine or a metal catalyst may be added to the coating solution in order to promote modification to the silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

  The addition amount of these catalysts is preferably adjusted to 2% by mass or less with respect to the polysilazane compound in order to avoid excessive silanol formation by the catalyst, reduction in film density, increase in film defects, and the like.

  In addition to the polysilazane compound, the coating liquid containing the polysilazane compound can contain an inorganic precursor compound. The inorganic precursor compound other than the polysilazane compound is not particularly limited as long as a coating liquid can be prepared. For example, paragraph numbers (0140) to (0142) of International Publication No. 2012/090644, International Publication No. 2013 / 002026 paragraph numbers (0112) to (0114), Japanese Patent Application Laid-Open No. 2015-33764 paragraph numbers (0072) to (0074), etc., including silicon-containing compounds and polysilsesquioxanes Can do.

(Vacuum ultraviolet light irradiation process)
The gas barrier layer according to the present invention is represented by a composition of SiO _x N _y as a whole layer by modifying at least a part of the polysilazane in the step of irradiating the coating film containing the polysilazane compound with vacuum ultraviolet light. A gas barrier layer containing silicon oxynitride is formed.

  For details of the vacuum ultraviolet light irradiation process, for example, paragraph numbers (0144) to (0155) of International Publication No. 2012/090644, paragraph numbers (0117) to (0134) of International Publication No. 2013/002026, JP, Conditions described in paragraph numbers (0102) to (0136) of 2015-33764 can be appropriately selected and adopted.

(Modification equipment using vacuum ultraviolet light)
Next, a method for forming a gas barrier layer using a reforming apparatus using vacuum ultraviolet light will be described with reference to the drawings.

  FIG. 5 is a schematic cross-sectional view showing an example of a vacuum ultraviolet light irradiation apparatus applicable to the formation of the gas barrier layer according to the present invention.

  In the vacuum ultraviolet light irradiation apparatus (100) shown in FIG. 5, reference numeral 101 denotes an apparatus chamber, which is supplied with appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausted from a gas discharge port (not shown). Water vapor can be substantially removed from the inside, and the oxygen concentration can be maintained at a predetermined concentration. Reference numeral 102 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 104 denotes a sample stage. The sample stage (104) can be reciprocated horizontally at a predetermined speed in the apparatus chamber (101) by a moving means (not shown). The sample stage (104) can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 105 denotes a sample on which a polysilazane coating layer is formed. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the surface of the sample coating layer and the excimer lamp tube surface is 3 mm. Reference numeral 106 denotes a light-shielding plate that prevents the vacuum ultraviolet light from being applied to the coating layer of the sample during the aging of the Xe excimer lamp (102).

  The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation step can be measured using a 172 nm sensor head using an ultraviolet integrated light meter: C8026 / H8025UVPOWERMETER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed at the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber (101) is a vacuum. Nitrogen and oxygen are supplied so that the oxygen concentration is the same as that in the ultraviolet irradiation step, and the sample stage (104) is moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp (102), it is preferable to provide an aging time of 10 minutes after the Xe excimer lamp is turned on, and then start the measurement by moving the sample stage.

As the gas barrier property of the gas barrier layer according to the present invention formed by the above method, water vapor permeability (abbreviation: WVTR, temperature: 38 ° C., relative humidity (measured by a method according to JIS K 7129-1992)) RH): 100%) is preferably 1.0 g / (m ² · 24 h) or less, more preferably 0.1 g / (m ² · 24 h) or less, and 0.01 g / (m ² -It is more preferable that it is 24h) or less.

[Other constituent layers of gas barrier film unit]
The gas barrier film unit according to the present invention may be provided with various functional layers as necessary in addition to the support and the gas barrier layer described above.

(Antistatic layer)
The antistatic layer containing an antistatic agent can impart a function of preventing the support from being charged when the gas barrier film laminate is handled.

  Specifically, it is possible to prevent charging by providing a layer containing an ion conductive substance or the like. The ion conductive substance here refers to a substance that shows electric conductivity and contains ions that are carriers for carrying electricity, and examples thereof include ionic polymer compounds.

  Examples of the ionic polymer compound include anionic polymer compounds as disclosed in JP-B-49-23828, JP-B-49-23827, JP-B-47-28937, and the like; Disclosed in Japanese Patent Publication No. 50-54772, Japanese Patent Publication No. 59-14735, Japanese Patent Publication No. 57-18175, Japanese Patent Publication No. 57-18176, Japanese Patent Publication No. 57-56059, etc. Ionene type polymer having a dissociating group in the main chain; Japanese Patent Publication No. 53-13223, Japanese Patent Publication No. 57-15376, Japanese Patent Publication No. 53-45231, Japanese Patent Publication No. 55-145783, Japanese Patent Publication No. 55-65950 Gazette, Japanese Patent Publication No. 55-67746, Japanese Patent Publication No. 57-11342, Japanese Patent Publication No. 57-19735, Japanese Patent Publication No. 58-56858 Publication Sho 61-27853 discloses, as disclosed in JP-B-62-9346 and the like, can be mentioned cationic pendant polymers having a cationic dissociative group in the side chain.

  Examples of the conductive substance include ionene conductive polymers as described in JP-A-9-203810, quaternary ammonium cation conductive polymer particles having intermolecular crosslinking, and the like.

  In addition, the crosslinked cationic conductive polymer as a dispersible granular polymer can have a high concentration and high density of the cation component in the particles, so that it has not only excellent conductivity but also low conductivity. There is no deterioration in conductivity even under relative humidity.

Examples of the antistatic agent include metal oxides that are conductive fine particles. For example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO _2. , V ₂ O ₅ or the like, or a composite oxide thereof is preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. As an example of containing a heteroatom, the addition Al, or In to ZnO, addition Nb, or Ta for TiO _2, or for the SnO _2, Sb, Nb, halogen elements etc. Is effective. The addition amount of these different atoms is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%, based on the total mass of the antistatic layer.

Further, the volume resistivity of these conductive metal oxide powders is 1 × 10 ⁷ Ωcm or less, particularly 1 × 10 ⁵ Ωcm or less, and the primary particle size is 100 μm to 0.2 μm. It is preferable that the antistatic layer contains 0.01 to 20% by volume of powder having a specific structure with a major axis of 30 nm to 6 μm.

  Examples of the resin used to hold the antistatic agent include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate, polyvinyl acetate, polystyrene, and polycarbonate. , Polyesters such as polybutylene terephthalate or copolybutylene / tere / isophthalate, polyvinyl alcohol derivatives such as polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, or polyvinyl benzal, norbornene polymers containing norbornene compounds, polymethyl methacrylate , Polyethyl methacrylate, polypropylyl methacrylate, polybutyl methacrylate, It can be used a copolymer of acrylic resin or an acrylic resin and other resins such as trimethyl acrylate but not particularly limited thereto. Among these, cellulose derivatives or acrylic resins are preferable, and acrylic resins are most preferably used.

  As the resin used for forming the antistatic layer, the above-mentioned thermoplastic resin having a weight average molecular weight exceeding 400,000 and a glass transition point of 80 to 110 ° C. is preferable in terms of optical properties and surface quality of the coating layer.

  The glass transition point can be determined by the method described in JIS K7121. The resin used here is 60% by mass or more, more preferably 80% by mass or more of the total resin used in the antistatic layer, and an actinic ray curable resin or a thermosetting resin is added as necessary. You can also do 10 things.

  These resins are coated in a state dissolved in an appropriate solvent as a binder for forming the antistatic layer.

  In the coating composition for coating the antistatic layer, hydrocarbons, alcohols, ketones, esters, glycol ethers, and the like can be appropriately mixed and used as a solvent. It is not limited to.

  Examples of the hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, Examples include pentanol, 2-methyl-2-butanol, and cyclohexanol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl formate, ethyl formate, and methyl acetate. , Ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, methyl lactate and the like. Examples of glycol ethers (C1 to C4) include methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether. (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, or propylene glycol mono (C1-C4) alkyl ether esters include propylene glycol monomethyl ether Examples of acetate, propylene glycol monoethyl ether acetate, and other solvents include N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

  In the present invention, as a method of applying the coating solution for forming the antistatic layer, doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating, or U.S. Pat. Examples include an extrusion coating method using a hopper described in the specification of US Pat. No. 2,681,294. By appropriately using these methods, it is possible to form an antistatic layer by coating so that the dry film thickness is preferably 0.1 to 20 μm, more preferably 0.2 to 5 μm.

[Clear hard coat layer]
In the gas barrier film unit according to the present invention, a clear hard coat layer can be provided between the support and the gas barrier layer or between the support and the above-described antistatic layer.

  As the clear hard coat layer, a curable resin such as a thermosetting resin or an active energy ray curable resin curable resin can be used. Of these, active energy ray-curable resins are preferred because they are easy to mold.

  The thermosetting resin is not particularly limited, and examples thereof include various thermosetting resins such as epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins. .

  Any epoxy resin may be used as long as it has an average of two or more epoxy groups per molecule. Specifically, it is a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl type epoxy resin, or a naphthol type epoxy. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin , Epoxy resin having a butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having a dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, diglycidyl alcohol Examples include etherified products, alkyl-substituted products of these epoxy resins, halides, hydrogenated products, and the like. These may be used alone or in combination of two or more.

  The active energy ray-curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams.

  Typical examples of the active energy ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, and among these, an ultraviolet curable resin is preferable.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. Can do.

  In addition, about the other details of a clear hard-coat layer, the conditions described in the paragraph numbers (0230)-(0246) of Unexamined-Japanese-Patent No. 2015-33764 etc. can be selected suitably, and can be employ | adopted, for example.

[Bleed-out prevention layer]
In the gas barrier film unit according to the present invention, a bleed-out preventing layer may be provided on the support surface opposite to the surface on which the gas barrier layer is provided.

  The bleed-out prevention layer is provided for the purpose of suppressing a phenomenon that, when the film is heated, unreacted oligomers and the like are transferred from the film to the surface and contaminate the contact surface.

  The unsaturated organic compound having a polymerizable unsaturated group that can be contained as a hard coat agent in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule. Alternatively, a monounsaturated organic compound having one polymerizable unsaturated group in the molecule can be exemplified.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable. As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination.

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

  The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  The bleed-out prevention layer as described above is mixed with a hard coat agent, a matting agent, and other components as necessary, and is prepared as a coating solution by using a diluent solvent as necessary, and supports the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure.

  In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer is in the range of 1.0 to 10 μm from the viewpoint of improving the heat resistance of the film, facilitating the balance adjustment of the optical properties of the film, and adjusting the curl of the gas barrier film. Is more preferable, and a range of 2 μm to 7 μm is more preferable.

  For the detailed configuration of the bleed-out prevention layer, for example, the contents described in paragraph numbers (0247) to (0261) of JP-A-2015-33764 can be referred to.

<Method for measuring characteristic values of gas barrier film unit>
The characteristic value of the gas barrier film unit according to the present invention can be measured according to the following method.

(Measurement of water vapor transmission rate)
The water vapor transmission rate of the gas barrier film can be measured according to the B method described in JIS K 7129 (1992). Specific examples of the method include a cup method, a wet / dry sensor method (Lassy method), and an infrared sensor method (mocon method). However, as the gas barrier properties are improved, these methods are used for measurement. The limit may be reached, and the following method has also been proposed.

<Measurement method of water vapor transmission rate other than above>
1. Ca method A method in which metal Ca is vapor-deposited on a gas barrier film and the phenomenon that the metal Ca is corroded by moisture that has passed through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.

  2. A method proposed by MORESCO Co., Ltd. (December 8, 2009, NewsRelease) A method of passing water vapor through a cold trap between a sample space under atmospheric pressure and a mass spectrometer in ultra-high vacuum.

  3. HTO method (General Atomics, USA) A method of calculating water vapor permeability using tritium.

  4). Method proposed by A-Star (Singapore) (International Publication No. 2005/95924) A material whose electrical resistance is changed by water vapor or oxygen (for example, Ca, Mg) is used for the sensor, and the electrical resistance change and its inherent 1 / F The method of calculating water vapor transmission rate from a fluctuation component.

  In the gas barrier film unit according to the present invention, the method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, the water vapor transmission rate measurement method is preferably measured by the following Ca method.

<Measurement of water vapor transmission rate by Ca method>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: YamatoHumicic ChamberIG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
Preparation of cell for evaluating water vapor barrier property Using a vacuum vapor deposition device (JEOL-made vacuum vapor deposition device JEE-400) on the gas barrier layer surface of the gas barrier film sample, vapor deposition of the barrier film sample before applying the transparent conductive film Masking is made except for the desired portion (9 locations of 12 mm × 12 mm), and metallic calcium is deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere Then, an evaluation cell is produced by irradiating with ultraviolet rays. In addition, in order to confirm the change in the gas barrier property before and after bending, a water vapor barrier property evaluation cell is similarly prepared for the barrier film that has not been subjected to the bending treatment.

  The obtained sample with both sides sealed was stored under high temperature and high humidity of 85 ° C. and 85% RH, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. Calculate moisture content.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, metal calcium is vapor-deposited using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample. The sample was stored under the same high temperature and high humidity conditions of 85 ° C. and 85% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 3000 hours.

The water vapor permeability of the gas barrier film unit according to the present invention is preferably as low as possible, but is preferably 0.001 to 0.00001 g / m ² · 24 h, for example, 0.0001 to 0.000001 g / m ^2. -More preferably 24h.

《Electronic device》
The electronic device of the present invention comprises the gas barrier film laminate of the present invention.

  The gas barrier film laminate according to the present invention can be preferably used for an electronic device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.

  As an example of an electronic device, electronic devices, such as an organic electroluminescent element (organic EL element), a liquid crystal display element (LCD), a thin-film transistor, a touch panel, electronic paper, a solar cell (PV), can be mentioned, for example. From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL device or a solar cell, and particularly preferably used for an organic EL device.

  The gas barrier film laminate of the present invention can also be used for device film sealing. That is, it is a method of providing the gas barrier film of the present invention on the surface of the device itself as a support. The device may be covered with a protective layer before providing the gas barrier film.

  The gas barrier film of the present invention can also be used as a device substrate or a film for sealing by a solid sealing method. The solid sealing method is a method in which after a protective layer is formed on a device, an adhesive layer and a gas barrier film are stacked and cured. Although there is no restriction | limiting in particular in an adhesive agent, A thermosetting epoxy resin, a photocurable acrylate resin, etc. are illustrated.

[Organic EL device]
The gas barrier film laminate of the present invention can be applied to an organic EL element. For the outline of the organic EL element applicable to the present invention, for example, JP2013-157634A and JP2013-168552A. JP, 2013-177361, JP 2013-187511, JP 2013-191644, JP 2013-191804, JP 2013-225678, JP 2013-235994 JP, 2013-243234, JP 2013-243236, JP 2013-242366, JP 2013-243371, JP 2013-245179, JP 2013-003249, JP 2014-003299 A, JP 2014-013910 A , JP 2014-017493 JP include a configuration described in JP-2014-017494 Patent Publication.

(Liquid crystal display element)
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier film of the present invention can be used as the transparent electrode substrate and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. The type of the liquid crystal cell is not particularly limited, but more preferably a TN type (Twisted Nematic), an STN type (Super Twisted Nematic), a HAN type (Hybrid Aligned Nematic), a VA type (Vertical Alignment), an EC type, a B type. OCB type (Optically Compensated Bend), IPS type (In-Plane Switching), and CPA type (Continuous Pinwheel Alignment) are preferable.

(Solar cell)
The gas barrier film of the present invention can also be used as a sealing film for solar cell elements. Here, the gas barrier film of the present invention is preferably sealed so that the gas barrier layer is closer to the solar cell element. The solar cell element in which the gas barrier film of the present invention is preferably used is not particularly limited, but for example, a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, or a tandem structure type Amorphous silicon-based solar cell elements, III-V group compound semiconductor solar cell elements such as gallium arsenide (GaAs) and indium phosphorus (InP), II-VI group compound semiconductor solar cell elements such as cadmium tellurium (CdTe), I / III-VI group compound semiconductor solar cells such as copper / indium / selenium (CIS), copper / indium / gallium / selenium (CIGS), copper / indium / gallium / selenium / sulfur (CIGS), etc. Examples include an element, a dye-sensitized solar cell element, and an organic solar cell element. Among these, in the present invention, the solar cell element is a copper / indium / selenium system (CIS system), a copper / indium / gallium / selenium system (CIGS system), a copper / indium / gallium / selenium / sulfur system (CIGSS system). It is preferable that it is an I-III-VI group compound semiconductor solar cell element.

(Other)
As other application examples, the thin film transistor described in JP-A-10-512104, the touch panel described in JP-A-5-127822, JP-A-2002-48913, etc., described in JP-A-2000-98326. Electronic paper and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<Production of gas barrier film laminate>
[Preparation of gas barrier film laminate 1]
[Production of gas barrier film unit UA1]
Transparent resin support with double-sided hard coat layer (intermediate layer) (1A, polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd.), hard coat layer is composed of UV curable resin mainly composed of acrylic resin Gas barrier layers 1 to 5 were laminated according to the following method on a PET thickness of 125 μm to produce a gas barrier film unit UA1.

(Formation of gas barrier layer 1: vacuum ultraviolet light modification treatment method)
In accordance with the following method, the gas barrier layer 1 was formed by a vacuum ultraviolet light modification treatment method.

<Preparation of polysilazane-containing coating solution 1>
A dibutyl ether solution containing 20% by mass of non-catalyzed perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and a dibutyl ether solution containing 20% by mass of perhydropolysilazane containing amine catalyst (AZ Electronic Materials ( Co., Ltd., NAX120-20) was mixed at a ratio of 4: 1, and further diluted with a dibutyl ether solvent so that the solid content of the coating solution was 5% by mass. Prepared.

<Formation of gas barrier layer>
The prepared polysilazane-containing coating solution 1 was coated on the support with a slot die coater so that the layer thickness after drying was 110 nm, and heat-treated at 80 ° C. to form a polysilazane coating film.

Subsequently, after forming a polysilazane coating film, according to the following method, vacuum ultraviolet light (MDI-Comm excimer irradiation apparatus MODEL: MECL-M-1-200, wavelength 172 nm, stage temperature 100 ° C., integrated light quantity 3000 mJ / The gas barrier layer 1 was formed by irradiation with cm ² and an oxygen concentration of 0.1%.

<Vacuum ultraviolet irradiation conditions>
The vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic sectional view of FIG.

  In the vacuum ultraviolet light irradiation apparatus (100) shown in FIG. 5, reference numeral 101 denotes an apparatus chamber, which is supplied with appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausted from a gas discharge port (not shown). Water vapor was substantially removed from the inside, and the oxygen concentration was maintained at a predetermined concentration. Reference numeral 102 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 103 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 104 denotes a sample stage. The sample stage 104 was reciprocated horizontally at a predetermined speed in the apparatus chamber 101 by a moving means (not shown). The sample stage 104 was maintained at 100 ° C. by a heating means (not shown). Reference numeral 105 denotes a sample on which a polysilazane coating is formed. When the sample stage moved horizontally, the height of the sample stage was adjusted so that the shortest distance between the sample coating layer surface and the excimer lamp tube surface was 3 mm.

  The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation step was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025UVPOWERMETER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is installed in the center of the sample stage 104 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 101 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as in the process, and the measurement was performed by moving the sample stage 104 at a speed of 0.5 m / min.

Based on the irradiation energy obtained by this measurement, it adjusted so that it might become 3000 mJ / cm < ² > irradiation energy by adjusting the moving speed of a sample stage. The vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.

(Formation of gas barrier layer 2: plasma CVD method)
Next, a gas barrier layer 2 was formed on the formed gas barrier layer 1 by the following plasma CVD method.

<Formation of gas barrier layer by plasma CVD method>
Using the discharge plasma chemical vapor deposition apparatus shown in FIG. 4, it was set in a plasma CVD film forming apparatus (31) and continuously conveyed by roll-to-roll. Next, a magnetic field is applied between the film formation roller (39) and the film formation roller (40), and electric power is supplied to the film formation roller (39) and the film formation roller (40), respectively. 39) and a film forming roller (40) to generate a plasma to form a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas), which is a reactive gas, is used as a film forming gas in a gas supply pipe (41). The gas barrier layer 2 having a layer thickness of 270 nm was formed on the support (1) having the gas barrier layer 1 supplied under the following conditions.

(Deposition conditions)
Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Reaction gas (O ₂ ) supply amount: 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 0.8 m / min
(Formation of gas barrier layer 3: vacuum ultraviolet light modification treatment method)
Next, on the formed gas barrier layer 2, the solid content of the coating liquid in the polysilazane-containing coating liquid is changed to 10% by mass in the same manner as in the preparation of the gas barrier layer 1, and the layer thickness after drying is 250 nm. The gas barrier layer 3 was formed in the same manner except that the integrated amount of vacuum ultraviolet light during modification was changed to 6500 mJ / cm ^2. did.

(Formation of gas barrier layer 4: vacuum ultraviolet light modification treatment method)
Next, the gas barrier layer 4 having a layer thickness of 250 nm was formed on the gas barrier layer 3 formed in the same manner as the production of the gas barrier layer 3.

(Formation of gas barrier layer 5: vacuum ultraviolet light modification treatment method)
Subsequently, the gas barrier layer 5 having a layer thickness of 250 nm was formed on the gas barrier layer 4 formed in the same manner as the production of the gas barrier layer 3.

[Production of gas barrier film unit UB1]
Transparent resin support with double-sided hard coat layer (intermediate layer) (1B, polyethylene terephthalate (PET) film with clear hard coat layer (CHC) manufactured by Kimoto Co., Ltd.) Hard coat layer is composed of UV curable resin mainly composed of acrylic resin The gas barrier layer 6 was formed on the PET by a plasma CVD method to produce a gas barrier film unit UB1.

(Formation of gas barrier layer 6: plasma CVD method)
On the support (1B), a gas barrier layer 6 having a layer thickness of 270 nm was formed by the same plasma CV method as used in the formation of the gas barrier layer 2.

[Bonding of Gas Barrier Film Unit UA1 (hereinafter referred to as Film Unit UA1) and Gas Barrier Film Unit UB1 (hereinafter referred to as Film Unit UB1) by an adhesive layer]
The produced film unit UA1 and film unit UB1 were bonded via a pressure sensitive adhesive according to the following method.

  On the surface opposite to the surface having the gas barrier layer (2A) of the support (1A) constituting the produced film unit UA1, 1 kg of pressure sensitive adhesive SK2147 manufactured by Soken Chemical Co., Ltd., and a curing agent TD The pressure-sensitive adhesive layer-forming material blended with -75 at a ratio of 0.4 g was applied under the condition that the film thickness after drying was 15 μm to form a pressure-sensitive adhesive layer (3).

  Next, the gas barrier layer (2B) surface of the film unit UB1 and the pressure-sensitive adhesive layer (3) formed above are transported at a speed of 3 m / min, the tension between the film unit UA1 and the film unit UB1 is 110 N / m, and the nip pressure. Bonding was performed under the condition of 25 kPa to produce a gas barrier film laminate 1 having the configuration shown in FIG.

[Measurement of adhesive strength in gas barrier film laminate 1]
The produced gas barrier film laminate 1 is cut to a width of 25 mm, and the adhesive surface (3 in FIG. 1) and the adhesive surface (1A in FIG. 1) of the film unit UA1 (FIG. 1) The cotton adhesion force at the interface A) described in 1 was measured by a method based on the peel strength of JIS Z 0237, which was peeled off by 90 degrees.

1) Measuring apparatus It measured by combining the following apparatus made from Imada Corporation.

Gauge; ZP-50N
Slad table; P90-200N
Stand; MX2-500N
2) Sample size: width 25mm
3) Measurement environment: 23 ± 1 ° C, relative humidity 50 ± 5%
The adhesive strength of the gas barrier film laminate 1 measured by the above method was 2.3 N / 25 mm.

[Preparation of gas barrier film laminate 2]
In the production of the gas barrier film laminate 1, the gas barrier film laminate 2 was prepared in the same manner except that the film unit UA1 and the film unit UB1 were bonded via an adhesive layer according to the following method. Produced.

  The produced film unit UA1 and film unit UB1 were bonded together using a pressure-sensitive adhesive “DK” (layer thickness: 25 μm) manufactured by Sanei Kaken Co., Ltd.

(First step: Application of adhesive layer to film unit UB1)
The separator film affixed on one surface side of the pressure sensitive adhesive DK is peeled off, and the peeled surface of the pressure sensitive adhesive and the gas barrier layer (2B) forming surface of the film unit UB1 are arranged in a facing position, Bonding was performed under the conditions that the conveyance speed was 3 m / min, the tension of the film unit UB1 was 110 N / m, and the nip pressure was 25 kPa.

(Second step: Application of adhesive layer to film unit UA1)
The separator film affixed to the other surface side of the pressure-sensitive adhesive DK is peeled off, and the peeled surface of the adhesive and the support (1A) of the film unit UA1 are placed facing each other, and the transport speed is The gas barrier film laminate 2 having the configuration shown in FIG. 1 was prepared by bonding under conditions of 3 m / min, a tension of the film unit UA1 of 110 N / m, and a nip pressure of 25 kPa. The adhesive strength at the interface A of the gas barrier film laminate 2 was 25 N / 25 mm.

[Preparation of gas barrier film laminate 3]
A gas barrier film laminate 3 was produced in the same manner as in the production of the gas barrier film laminate 2 except that the thickness of the pressure-sensitive adhesive layer was changed to 50 μm. The adhesive force at the interface A of the gas barrier film laminate 3 was 32 N / 25 mm.

[Preparation of gas barrier film laminate 4]
In the production of the film unit UA1 constituting the gas barrier film laminate 1, the transparent resin support (1B, PET, thickness 125 μm) used for the production of the film unit UB1 was used as the transparent resin support (1B, PET, A gas barrier film laminate 4 was prepared in the same manner except that the thickness was changed to 50 μm). The adhesive strength at the interface A of the gas barrier film laminate 4 was 2.3 N / 25 mm.

[Preparation of gas barrier film laminate 5]
In the production of the gas barrier film laminate 2, the gas barrier was similarly changed except that the type of the pressure sensitive adhesive was changed from “DK” manufactured by Sanei Kaken Co., Ltd. to “PDS1” manufactured by Panac Co., Ltd. Film laminate 5 was prepared. The adhesive strength at the interface A of the gas barrier film laminate 5 was 5.4 N / 25 mm.

[Preparation of gas barrier film laminate 6]
The produced film unit UA1 and film unit UB1 were bonded via a pressure sensitive adhesive according to the following method.

  On the surface opposite to the surface having the gas barrier layer (2A) of the support (1A) constituting the produced film unit UA1, 10 kg of a pressure sensitive adhesive LIS-825 manufactured by Toyo Morton Co., Ltd., and CAT A pressure-sensitive adhesive layer (3) was formed on the pressure-sensitive adhesive layer forming material containing 1 kg of RT85 and 8 kg of ethyl acetate as a solvent under the condition that the film thickness after drying was 5 μm.

  Next, after the film unit UA1 with the pressure-sensitive adhesive layer formed is stored for 3 months in an environment of 23 ° C. and 55% RH, the gas barrier layer (2B) surface of the film unit UB1 and the pressure-sensitive adhesive layer (3) formed above Were bonded under the conditions of a conveyance speed of 3 m / min, a tension of the film unit UA1 and the film unit UB1 of 110 N / m, and a nip pressure of 25 kPa, thereby producing a gas barrier film laminate 6. The adhesive strength at the interface A of the gas barrier film laminate 6 was 3.2 N / 25 mm.

[Preparation of gas barrier film laminate 7]
Using the LED type line UV irradiator “Aicure UD40” manufactured by Panasonic on the surface opposite to the surface having the gas barrier layer (2A) of the support (1A) constituting the produced film unit UA1. UV treatment was performed under the condition of 4200 mW / cm ² .

  Next, the pressure-sensitive adhesive LIS-825 manufactured by Toyo Morton Co., Ltd., 10 kg, CAT-RT85 1 kg, and a solvent layer forming material containing 8 kg of ethyl acetate as a solvent on the surface subjected to UV treatment, The pressure-sensitive adhesive layer (3) was formed under the condition that the film thickness after drying was 11 μm.

  Next, after the film unit UA1 with the pressure-sensitive adhesive layer formed is stored for 3 months in an environment of 23 ° C. and 55% RH, the gas barrier layer (2B) surface of the film unit UB1 and the pressure-sensitive adhesive layer (3) formed above Were bonded under the conditions of a conveyance speed of 3 m / min, a tension of the film unit UA1 and the film unit UB1 of 110 N / m, and a nip pressure of 25 kPa, thereby producing a gas barrier film laminate 7. The adhesive strength at the interface A of the gas barrier film laminate 7 was 10 N / 25 mm.

[Preparation of gas barrier film laminate 8]
In the production of the gas barrier film laminate 5, the PDS1-15HU75 made by Panac Co., Ltd. was used as the pressure-sensitive adhesive layer forming material, and the layer thickness was changed to 15 μm. Produced. The adhesive strength at the interface A of the gas barrier film laminate 8 was 15 N / 25 mm.

[Production of gas barrier film laminate 9]
A gas barrier film laminate 9 was prepared in the same manner as in the production of the gas barrier film laminate 6 except that the thickness of the pressure-sensitive adhesive layer was changed to 19 μm. The adhesive strength at the interface A of the gas barrier film laminate 9 was 18 N / 25 mm.

[Production of gas barrier film laminate 10]
A gas barrier film laminate 10 was produced in the same manner as in the production of the gas barrier film laminate 6 except that the thickness of the pressure-sensitive adhesive layer was changed to 22 μm. The adhesive strength at the interface A of the gas barrier film laminate 10 was 20 N / 25 mm.

[Preparation of Gas Barrier Film Laminate 11]
In the production of the gas barrier film laminate 8, the gas unit was similarly formed except that an antistatic layer was formed on the support (1B) surface side of the film unit UB1 by sputtering, which is the following vacuum film formation method. A barrier film laminate 11 was produced. The adhesive strength at the interface A of the gas barrier film laminate 11 was 15 N / 25 mm.

(Formation of antistatic layer)
After producing the film unit UB1, the surface of the support (1B) was passed through a drum heated to 150 ° C., and ZnO was used as a target, under conditions of a degree of vacuum of 1.33 Pa and a deposition rate of 5 m / min. An antistatic layer formed of a ZnO film having a thickness of 140 nm at 5 kW was provided by introducing a gas having an oxygen fraction of 1.0 volume% of the film gas and using an Rf magnetron sputtering method.

[Production of gas barrier film laminate 12]
In the production of the gas barrier film laminate 8, the support (1A) constituting the film unit UA1 is a transparent resin support with a double-sided hard coat layer (intermediate layer) (PET film manufactured by Kimoto, thickness: 50 μm). A gas barrier film laminate 12 was produced in the same manner except that the gas barrier film laminate 12 was changed. The adhesive strength at the interface A of the gas barrier film laminate 12 was 15 N / 25 mm.

[Production of Gas Barrier Film Laminate 13]
In the production of the film unit UA1 constituting the gas barrier film laminate 12, the transparent resin support (PET, thickness 50 μm) was changed to Cosmo Shine A4300 (PET, thickness 38 μm) manufactured by Toyobo Co., Ltd. In the same manner, a gas barrier film laminate 13 was produced. The adhesive strength at the interface A of the gas barrier film laminate 13 was 15 N / 25 mm.

[Production of gas barrier film laminate 14]
In the production of the gas barrier film laminate 11, the gas barrier film laminate is similarly produced except that the film forming method of the gas barrier layer (2B) constituting the film unit UB1 is changed to the sputtering method shown below. 14 was produced. The adhesive strength at the interface A of the gas barrier film laminate 14 was 15 N / 25 mm.

(Formation of gas barrier layer (2B) of film unit UB1)
By sputtering using a sputtering target (Mitsubishi Materials Corp. target, ST-IV series) while passing through a drum heated to 150 ° C. by vacuum film-forming sputtering. Sputtering was performed to form a gas barrier layer made of a SiO ₂ film having a thickness of 120 nm.

<< Production of Electronic Device: Production of Organic EL Element >>
Each constituent layer of the organic EL element is laminated according to the following method on the gas barrier layer (2A) of the film unit UA1 of each gas barrier film laminate produced as described above, and has the configuration shown in FIG. Organic EL elements 1 to 14 were produced.

[Production of Organic EL Element 1]
(Formation of first electrode layer)
On the gas barrier layer (2A) of the film unit UA1 of the gas barrier film laminate 1, an ITO (indium tin oxide) film having a thickness of 150 nm is formed by sputtering, patterned by photolithography, and the first electrode. A layer was formed. The pattern was such that the light emission area was 50 mm square.

(Formation of hole transport layer)
On the first electrode layer of the gas barrier film laminate 1 on which the first electrode layer is formed, the following coating liquid for forming a hole transport layer is applied by an extrusion coater, and then dried to transport holes. A layer was formed. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Before applying the coating solution for forming the hole transport layer, as a cleaning and surface modification treatment of the gas barrier film laminate 1, a low-pressure mercury lamp with a wavelength of 184.9 nm is used, an irradiation intensity of 15 mW / cm ² , a distance Conducted at 10 mm. For the charge removal treatment, a static eliminator using weak X-rays was used.

<Application conditions>
The coating process was performed in an atmosphere of 25 ° C. and a relative humidity of 50% RH.

<Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron PAI4083 manufactured by Bayer) with 65% pure water and 5% methanol was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent is removed at a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C., followed by heat treatment. The back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using an apparatus to form a hole transport layer.

(Formation of light emitting layer)
Subsequently, on the hole transport layer of the gas barrier film laminate 1 formed up to the hole transport layer, the following coating solution for forming a white light emitting layer was applied by an extrusion coater, and then dried to form a light emitting layer. . The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of the following HA, 100 mg of the following DA, which is a dopant material, 0.2 mg of the following DB, which is a dopant material, and 0. 2 mg was dissolved in 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

<Drying and heat treatment conditions>
After the white light emitting layer forming coating solution was applied, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. Next, heat treatment was performed at a temperature of 130 ° C. to form a light emitting layer.

(Formation of electron transport layer)
Next, the following coating liquid for forming an electron transport layer was applied by an extrusion coater and then dried to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving the following EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, the solvent was removed at a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Next, in the heat treatment section, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
Next, an electron injection layer was formed on the formed electron transport layer. First, the sample formed up to the electron transport layer was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Except for the portion that becomes the extraction electrode on the first electrode, aluminum is used as the second electrode forming material on the formed electron injection layer under a vacuum of 5 × 10 ⁻⁴ Pa so as to have the extraction electrode Then, a mask pattern was formed by vapor deposition so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
The gas barrier film laminate 1 formed up to the second electrode was moved again to a nitrogen atmosphere and cut into a specified size using an ultraviolet laser.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
A sealing member was adhered to the organic EL element to which the electrode lead (flexible printed circuit board) was connected using a commercially available roll laminating apparatus, and the organic EL element 1 was manufactured.

  In addition, as a sealing member, a polyethylene terephthalate (PET) film (PET) film (on Toyo Aluminum Co., Ltd.) on a 30 μm-thick aluminum foil using a dry lamination adhesive (two-component reaction type urethane adhesive). 12 μm thick) (adhesive layer thickness 1.5 μm) was used.

  Using a dispenser, a thermosetting adhesive was uniformly applied to the aluminum surface with a thickness of 20 μm along the adhesive surface (shiny surface) of the aluminum foil.

  The following epoxy adhesives were used as the thermosetting adhesive.

Bisphenol A diglycidyl ether (DGEBA)
Dicyandiamide (DICY)
Epoxy adduct curing accelerator.

  Thereafter, the sealing substrate is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and pressure bonding conditions using a pressure bonding roll: pressure bonding temperature 120 ° C., pressure 0.5 MPa, apparatus speed 0. Adherent sealing was performed at 3 m / min.

[Preparation of organic EL elements 2 to 14]
In the production of the organic EL element 1, organic EL elements 2 to 14 were produced in the same manner except that the gas barrier film laminate 1 was changed to the gas barrier film laminates 2 to 14, respectively.

<< Evaluation of gas barrier film laminate >>
[Evaluation of crack resistance]
Each of the gas barrier film laminates produced above was subjected to a bending operation 1000 times at an angle of 180 ° on a SUS roll so that the film unit UA1 surface was inward and the radius was 3 mm. Next, the film unit UA1 is turned to the outside, the film is bent 1000 times at an angle of 180 ° so that the radius is 3 mm, and after 2000 times of bending is repeated, the gas barrier film unit is magnified 200 times with a microscope. The surface conditions of the gas barrier layer (2A) of UA and the gas barrier layer (2B) of the gas barrier film unit UB were observed at 200 times using an optical microscope, and crack resistance was evaluated according to the following criteria.

5: No cracks are observed in the gas barrier layers 2A (front surface) and 2B (back surface). 4: Slight cracks are generated on the one side of the gas barrier layer. No quality 3: Small cracks are generated in the gas barrier layers 2A and 2B, but the quality is acceptable for practical use 2: Small-sized cracks are generated in the gas barrier layers 2A and 2B. The quality of concern is 1: Many cracks are generated on the entire surface of the gas barrier layers 2A and 2B, and the quality is unpractical. [Evaluation of water vapor barrier properties]
In the evaluation of the crack resistance, each gas barrier film laminate subjected to 2000 times of bending treatment was immersed in hot water at 90 degrees for 30 minutes and then left in an 80 degree constant temperature bath for 1 hour.

  The water vapor barrier property was evaluated on behalf of the gas barrier layer (2A) of the film unit UA1. Metallic calcium with a thickness of 80 nm was deposited on the gas barrier layer (2A) of the film unit UA1, and the time when the formed calcium was 50% area was defined as 50% area time by the following method. .

(Metal calcium film forming equipment)
Vapor deposition apparatus: manufactured by JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: YamatoHumicic ChamberIG47M
(raw materials)
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation sample)
Using a vacuum deposition apparatus (vacuum deposition apparatus JEE-400 manufactured by JEOL Ltd.), metal calcium is deposited on the surface of the outermost gas barrier layer (2A) of the produced gas barrier film laminate through a mask in a size of 12 mm x 12 mm. I let you. At this time, the deposited film thickness was set to 80 nm.

  Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, and it is immediately transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum vapor-deposited surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX Corporation). The water vapor barrier property evaluation sample was produced by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.

  The obtained sample was stored at a high temperature and high humidity of 85 ° C. and 85% RH, and the state in which the metal calcium was corroded with respect to the storage time was observed. The observation was obtained by linearly interpolating the time at which the area where metal calcium was corroded with respect to the metal calcium vapor deposition area of 12 mm × 12 mm to 50% from the observation results.

  This was done by evaluating the time for the corrosion rate to reach an area of 50% as the degradation time. The longer the time, the better the gas barrier property.

<< Evaluation of organic EL elements >>
Each of the produced organic EL elements was evaluated for durability according to the following method.

[Evaluation of durability]
(Accelerated deterioration processing)
Each of the produced organic EL elements was subjected to an accelerated deterioration treatment for 100 hours in an environment of 85 ° C. and 85% RH, and then evaluated for the following black spots together with the organic EL elements not subjected to the accelerated deterioration treatment. .

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. A part of the panel was magnified with a Moritex MS-804 and a lens MP-ZE25-200) and photographed. The photographed image was cut out in a 2 mm square, the black spot generation area ratio was determined, the element deterioration resistance rate was calculated according to the following formula, and the durability was evaluated according to the following criteria. If the evaluation rank was greater than or equal to ◯, it was determined to be a practically preferable characteristic.

Element deterioration tolerance rate = (area of black spots generated in elements not subjected to accelerated deterioration processing / area of black spots generated in elements subjected to accelerated deterioration processing) × 100 (%)
A: Element degradation resistance ratio is 98% or more. O: Element degradation resistance ratio is 90% or more. .DELTA .: Element degradation resistance ratio is 60% or more and less than 90%. 20% or more and less than 60% x: The element deterioration resistance rate is less than 20% Table 2 shows the results obtained.

  As is clear from the results shown in Table 2, the present invention was prepared by bonding two gas barrier film units with an adhesive layer having an adhesive strength specified in the present invention in the range of 3 to 20 N / 25 mm. In the gas barrier film laminate of the invention, compared to the comparative example, even when the gas barrier layer is subjected to stress by an operation such as bending, the stress to the gas barrier layer is dispersed, and cracks are generated in the gas barrier layer. It is suppressed, and thereby high gas barrier properties can be maintained. Furthermore, by applying the gas barrier film laminate of the present invention to an electronic device (organic EL element), even after being stored for a long time in a harsh environment, the influence on the organic EL element is prevented and excellent. Durability can be obtained.

DESCRIPTION OF SYMBOLS 1, 1A, 1B Support body 2A, 2B Gas barrier layer 3 Adhesive layer 4 Anode 5, 7 Carrier transport functional layer 6 Light emitting layer 8 Cathode 9 Sealing adhesive layer 10 Sealing substrate 17 Vacuum pump 31 Roller discharge plasma CVD Device 32 Delivery roller 33, 34, 35, 36 Transport roller 39, 40 Film forming roller 41 Film forming gas supply pipe 42 Power source for generating plasma 43, 44 Magnetic field generating device 45 Winding roller 100 Vacuum ultraviolet light irradiation device 101 Device chamber 102 Xe excimer lamp 103 excimer lamp holder 104 sample stage 105 polysilazane coating layer formation sample 106 light shielding plate C chamber D electronic device EL organic EL element GF gas barrier film laminate UA, UB gas barrier film unit

Claims (7)

A gas barrier film laminate comprising at least two gas barrier film units each composed of a support and a gas barrier layer, each laminated via an adhesive layer,
The gas barrier film laminate according to claim 1, wherein the pressure-sensitive adhesive layer defined below has a pressure-sensitive adhesive force within a range of 3 to 20 N / 25 mm with respect to at least one of the gas barrier film units.
Adhesive strength: 90 ° peel-off adhesive strength measured in accordance with JIS Z 0237: 2009 under conditions of 23 ± 1 ° C. and relative humidity 50 ± 5%   The gas barrier film laminate according to claim 1, wherein the pressure-sensitive adhesive layer has an adhesive strength in the range of 5 to 18 N / 25 mm.   One surface side of the pressure-sensitive adhesive layer is in contact with a support constituting one gas barrier film unit, and the other surface side of the pressure-sensitive adhesive layer is in contact with a gas barrier layer constituting the other gas barrier film unit. It is a structure, The gas barrier film laminated body of Claim 1 or Claim 2 characterized by the above-mentioned.   The gas barrier film according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer is a pressure-sensitive pressure-sensitive adhesive layer and has a thickness of 15 to 30 µm. Laminated body.   The gas barrier film laminate according to any one of claims 1 to 4, wherein at least one of the gas barrier film units has an antistatic layer.   The thickness of the at least 1 support body which comprises the said gas-barrier film unit exists in the range of 20-50 micrometers, The gas barrier as described in any one of Claim 1-5 characterized by the above-mentioned. Film laminate.   An electronic device comprising the gas barrier film laminate according to any one of claims 1 to 6.

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