JP6705375B2 - Electronic device - Google Patents

Description

The present invention relates to electronic devices.

Conventionally, a gas barrier film formed by laminating multiple layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film, blocks various gases such as water vapor and oxygen. It is widely used for the packaging of articles that require, for example, packaging applications for preventing the deterioration of foods, industrial supplies, pharmaceuticals and the like.

In addition to packaging applications, the gas barrier film is required to be applied to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements and liquid crystal display elements, and many studies have been made. However, these flexible electronic devices are required to have a very high glass-barrier level gas barrier property and a property of not breaking (impact resistance).

As a method of forming a gas barrier film, JP 2013-61507 A proposes a method of laminating a plurality of gas barrier films or a method of forming gas barrier layers on both surfaces of a base material.

Further, in Japanese Patent Laid-Open No. 2013-241023 (corresponding to US Patent Application Publication No. 2011/039097), a gas barrier including a flexible film-shaped thin film glass substrate or a composite substrate of thin film glass and a resin film. Films have been proposed.

However, the gas barrier film described in JP 2013-61507 A has a high gas barrier that suppresses the occurrence of dark spots in an organic EL element under high temperature and high humidity conditions such as 85° C. and 85% RH. There was a problem that it did not reach sex. Further, the gas barrier film described in JP-A-2013-241023 (corresponding to U.S. Patent Application Publication No. 2011/039097) has a problem that it is easily cracked and is inferior in impact resistance.

Therefore, it is an object of the present invention to provide an electronic device having excellent durability in a high temperature and high humidity environment and excellent impact resistance.

The present inventor has earnestly studied to solve the above problems. As a result, a gas barrier property including (A) first gas barrier layer, (B) buffer layer, (C) second gas barrier layer, (D) third gas barrier layer, and (E) fourth gas barrier layer in this order It has been found that an electronic device including a film and the electronic device main body provided on the (E) fourth gas barrier layer can solve the above problems. The present invention has been completed based on the above findings.

That is, the present invention includes (A) a first gas barrier layer containing an inorganic compound; (B) a buffer layer containing a resin and having a thickness of 10 to 200 μm; (C) a second gas barrier layer containing an inorganic compound; (D) SiO _w N _x (wherein 0.2<w≦0.55, 0.66<x≦0.75) satisfying the composition range and having a thickness of 50 to 1000 nm No. 3 gas barrier layer: (E) SiO _y N _z (provided that 0.55<y≦2.0, 0.25<z≦0.66) is satisfied, and the gas barrier layer has a thickness of 8 to 200 nm. A fourth gas barrier layer having a thickness; in that order, a gas barrier film, and an electronic device body formed on the surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer. And an electronic device including.

It is a schematic diagram which shows an example of the film-forming apparatus which can be conveniently utilized for manufacturing the 1st gas barrier layer and the 2nd gas barrier layer of the gas barrier film which concerns on this invention, 1 is a base material. 10 is a delivery roll, 11, 12, 13, and 14 are conveying rolls, 15 is a first film forming roll, 16 is a second film forming roll, 17 is a winding roll, 18 is a gas supply pipe, 19 is a power source for plasma generation, 20 and 21 are magnetic field generators, 30 is a vacuum chamber, 40 is a vacuum pump, 41 is a control unit, S is S It is a film forming space. It is a schematic diagram which shows the other example of the film-forming apparatus which can be conveniently utilized for manufacturing the 1st gas barrier layer and the 2nd gas barrier layer of the gas barrier film which concerns on this invention, 1 is a base material. 10 is a delivery roll, 11, 12, 12′, 13, 13′ and 14 are transport rolls, 15 is a first film forming roll, 16 is a second film forming roll, and 15 'Is a third film forming roll, 16' is a fourth film forming roll, 17 is a take-up roll, 18 and 18' are gas supply pipes, 19 and 19' are plasma generating power supplies. Yes, 20, 20′, 21 and 21′ are magnetic field generators, 30 is a vacuum chamber, 40 is a vacuum pump, 41 is a control unit, and S and S′ are film formation spaces. ..

The present invention includes (A) a first gas barrier layer containing an inorganic compound; (B) a buffer layer containing a resin and having a thickness of 10 to 200 μm; (C) a second gas barrier layer containing an inorganic compound; ) SiO _w N _x (provided that 0.2<w≦0.55, 0.66<x≦0.75) satisfies the composition range and has a third thickness of 50 to 1000 nm. Gas barrier layer: (E) SiO _y N _z (provided that 0.55<y≦2.0, 0.25<z≦0.66) is satisfied, and a thickness of 8 to 200 nm. A fourth gas barrier layer having a gas barrier film in this order, and an electronic device body formed on the surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer, Including an electronic device. The electronic device of the present invention having such a configuration has excellent durability in a high temperature and high humidity environment and excellent impact resistance. In particular, when an organic EL element is used as the electronic device body, the electronic device is one in which the generation of dark spots is suppressed.

Hereinafter, preferred embodiments of the present invention will be described. The present invention is not limited to the following embodiments. Also, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from the actual ratios.

In the present specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, operations and measurements of physical properties are carried out under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50%.

[(A) First Gas Barrier Layer]
The (A) first gas barrier layer (hereinafter, also simply referred to as a layer (A)) according to the present invention contains an inorganic compound. Since the layer (A) is a layer that is exposed to the highest humidity condition among the layers (A) to (E), the composition is unlikely to change due to humidity and stably exhibits gas barrier properties. It is preferably formed by a vapor phase film forming method.

The first gas barrier layer according to the present invention contains an inorganic compound. The inorganic compound contained in the first gas barrier layer is not particularly limited, but examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides, and metal oxycarbides. Among them, in terms of gas barrier performance, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta. Can be preferably used, and oxides, nitrides or oxynitrides of metals selected from Si, Al, In, Sn, Zn and Ti are more preferable, and of metals selected from Si, Al and Ti, Oxides, nitrides or oxynitrides are preferred. Specific examples of suitable inorganic compounds include composites such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide, and aluminum silicate. Other elements may be contained as a secondary component.

The content of the inorganic compound contained in the first gas barrier layer is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and 95% by mass in the first gas barrier layer. The amount is more preferably the above, particularly preferably 98% by mass or more, and most preferably 100% by mass (that is, the first gas barrier layer is made of an inorganic compound).

The method for forming the first gas barrier layer is preferably a vapor deposition method such as physical vapor deposition (PVD method) and chemical vapor deposition (CVD method).

The vapor deposition method will be described below.

<Vapor deposition method>
A physical vapor deposition method (Physical Vapor Deposition, PVD method) is a method of depositing a target substance, for example, a thin film such as a carbon film, by a physical technique on the surface of the substance in a vapor phase. Examples thereof include a DC sputtering method, an RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method, a vacuum vapor deposition method, and an ion plating method.

The sputtering method is a method in which a target is set in a vacuum chamber, and a rare gas element (usually argon) ionized by applying a high voltage is made to collide with the target to repel atoms on the target surface and adhere them to a substrate. .. At this time, a reactive sputtering method may be used in which an element ejected from the target by the argon gas is reacted with nitrogen or oxygen by flowing nitrogen gas or oxygen gas into the chamber to form an inorganic layer. ..

The chemical vapor deposition (CVD) method is a method in which a source gas containing a target thin film component is supplied onto a substrate and a film is deposited by a chemical reaction on the substrate surface or in a vapor phase. Is. Further, there is a method of generating plasma or the like for the purpose of activating a chemical reaction, and known CVD methods such as a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, a vacuum plasma CVD method, and an atmospheric pressure plasma CVD method. A method etc. are mentioned. Although not particularly limited, it is preferable to apply a plasma CVD method such as a vacuum plasma CVD method or an atmospheric pressure plasma CVD method from the viewpoint of the film forming rate and the processing area.

For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is produced. This is because very active charged particles and active radicals are present in the plasma space at a high density, so that multi-step chemical reactions are promoted very rapidly in the plasma space, and elements existing in the plasma space are thermodynamically This is because it is converted into a stable compound in a very short time.

In the following description, a case where the first gas barrier layer is manufactured by using an opposed roll type roll-to-roll film forming device that forms a thin film by a plasma CVD method will be described as an example. To do.

1 and 2 are schematic configuration diagrams showing an example of a film forming apparatus. The film forming apparatus 101 illustrated in FIG. 2 is based on a configuration in which two film forming apparatuses 100 illustrated in FIG. 1 are joined in tandem. Here, the case of forming the gas barrier layer will be described by taking the film forming apparatus illustrated in FIG. 2 as an example, but the description of the film forming apparatus illustrated in FIG. 2 is different from the description of the film forming apparatus illustrated in FIG. However, it will be properly considered.

As shown in FIG. 2, the film forming apparatus 101 includes a delivery roll 10, conveying rolls 11 to 14, first, second, third and fourth film forming rolls 15, 16, 15 ′ and 16 ′, and a winding roll. Taking roll 17, gas supply pipes 18 and 18', plasma generating power supplies 19 and 19', magnetic field generators 20, 21, 20' and 21', vacuum chamber 30, and vacuum pumps 40 and 40'. , And a control unit 41.

The delivery roll 10, the transport rolls 11 to 14, the first, second, third and fourth film forming rolls 15, 16, 15 ′, 16 ′, and the winding roll 17 are housed in a vacuum chamber 30.

The temperature of the first to fourth film forming rolls 15, 16, 15', 16' is not particularly limited and is, for example, -30 to 100°C. If the glass transition temperature of the substrate 1a or lower, thermal deformation of the substrate can be suppressed.

A plasma generating power source 19 is used for the first film forming roll 15 and the second film forming roll 16, and a plasma generating power source 19' is used for the third film forming roll 15' and the fourth film forming roll 16'. A high frequency voltage for generation is applied. The voltage applied by the plasma generation power supply 19 and the voltage applied by the plasma generation power supply 19' may be the same or different. The power supply frequency of the plasma generating power supply 19 or 19' can be set arbitrarily, but the device of this configuration has, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 1 m for an effective film formation width. It is 10 kW.

When the (A) first gas barrier layer is formed using the film forming apparatus 101, the substrate 1a is transported in the forward direction and the reverse direction to reciprocate the film forming section S or the film forming section S′, The step (A) of forming (depositing) the first gas barrier layer may be repeated a plurality of times.

The gas supply pipes 18 and 18 ′ supply a film forming gas such as a raw material gas for plasma CVD into the vacuum chamber 30. The film forming gas supplied from the gas supply pipe 18 and the film forming gas supplied from the gas supply pipe 18' may be the same or different. Further, the supply gas pressures supplied from these gas supply pipes may be the same or different.

A silicon compound can be used as the source gas. Further, the compounds described in paragraph “0075” of JP-A-2008-056967 can also be used. Among the silicon compounds, hexamethyldisiloxane (HMDSO) is preferably used in the formation of the (A) first gas barrier layer, from the viewpoints of easy handling of the compound and high gas barrier properties of the obtained gas barrier film. .. Two or more kinds of silicon compounds may be used in combination. Further, the source gas may contain monosilane in addition to the silicon compound.

As the film forming gas, a reaction gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to form a silicon compound such as an oxide or a nitride is selected. As the film forming gas, a carrier gas may be further used to supply the source gas into the vacuum chamber 30. Further, as the film forming gas, a discharge gas may be further used to generate plasma.

The pressure (vacuum degree) in the vacuum chamber 30 can be appropriately adjusted according to the type of raw material gas. The pressure in the film forming section S or S'is preferably 0.1 to 50 Pa.

The first gas barrier layer may be a single layer or a laminated structure of two or more layers. When the first gas barrier layer has a laminated structure of two or more layers, the first gas barrier layers may have the same composition or different compositions.

The thickness of the first gas barrier layer (total thickness in the case of a laminated structure of two or more layers) is not particularly limited, but is preferably 10 to 2000 nm, and more preferably 30 to 1000 nm. Within this range, the gas barrier layer will have little or no cracks, and the gas barrier properties suitable for the present invention can be obtained.

[(B) Buffer layer]
The (B) buffer layer (hereinafter, also simply referred to as a layer (B)) according to the present invention is a layer containing a resin and having a thickness of 10 to 200 μm. The buffer layer having such a structure diffuses the moisture that has permeated the layer (A) in the buffer layer to create a low humidity state. By diffusing the moisture in this way, it is possible to make it difficult for the moisture to pass through and play a role of suppressing moisture permeation.

As such a buffer layer, a film containing a resin, that is, a resin base material is preferably used. Specific examples of the resin base material include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyether. Imide resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolephin copolymer, fluorene ring modified polycarbonate resin, fat Examples include base materials containing a thermoplastic resin such as a ring-modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound. The resin base material may be used alone or in combination of two or more kinds.

Since the gas barrier film according to the present invention is used as an electronic device such as an organic EL element, the resin base material is preferably transparent.

The resin base material preferably has a high surface smoothness. As the surface smoothness, it is preferable that the average surface roughness (Ra) is 2 nm or less. There is no particular lower limit, but in practice, it is preferably 0.01 nm or more. If necessary, the surface of the substrate may be polished to improve the smoothness.

The surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the treatments may be combined as necessary. You may go.

In addition to the above resin base material, a hard coat layer may be used as a buffer layer. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray-curable resin, but the active energy ray-curable resin is preferable because it is easy to mold. Such curable resins may be used alone or in combination of two or more.

Examples of commercially available active energy ray-curable resins used for forming the hard coat layer include, in addition to the above, for example, Hitaroid (registered trademark) series (manufactured by Hitachi Chemical Co., Ltd.), Shikko series (Nippon Synthetic Chemical Industry Co., Ltd.). Company), ETERMER 2382 (manufactured by ETERNAL CHEMICAL), and the like.

The buffer layer according to the present invention may have an adhesive layer. The adhesive layer is preferably used in the method (4) or (5) described later in the method for manufacturing an electronic device of the present invention.

The pressure-sensitive adhesive contained in the adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesive, silicon pressure-sensitive adhesive, urethane pressure-sensitive adhesive, polyvinyl butyral pressure-sensitive adhesive, ethylene-vinyl acetate pressure-sensitive adhesive, etc. can do. Further, examples of the adhesive contained in the tacky adhesive layer include an epoxy adhesive and a urethane adhesive. In this adhesive layer, as an additive, for example, a stabilizer, a surfactant, an ultraviolet absorber, a flame retardant, an antistatic agent, an antioxidant, a heat stabilizer, a lubricant, a filler, a coloring agent, an adhesion modifier, etc. Can be included.

The buffer layer may be a single layer or a laminated structure of two or more layers. When the buffer layer has a laminated structure of two or more layers, the buffer layers may have the same composition or different compositions.

The thickness of the buffer layer according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is 10 to 200 μm. If the thickness is less than 10 μm, diffusion of water that has permeated the first gas barrier layer may be insufficient, a passage for water may be formed, and water may easily permeate. On the other hand, when the thickness exceeds 200 μm, water may penetrate from the end (edge) of the buffer layer and shrink from the edge may occur. The thickness of the buffer layer is preferably 20 to 150 μm.

[(C) Second Gas Barrier Layer]
The (C) second gas barrier layer (hereinafter, also simply referred to as the layer (C)) according to the present invention contains an inorganic compound, similarly to the (A) first gas barrier layer. Since the type of the inorganic compound and the content of the inorganic compound contained in the second gas barrier layer are the same as those in the above (A) first gas barrier layer, the description thereof is omitted here.

The method for forming the second gas barrier layer is not particularly limited, but a vapor phase film forming method such as a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method), or an inorganic compound, preferably a silicon compound. More preferably, a method of applying energy to a coating film obtained by applying and drying a coating solution containing polysilazane (hereinafter, also simply referred to as a coating film forming method) and the like can be mentioned. Among these, the vapor phase film formation method is preferable from the viewpoint that the composition is unlikely to change due to humidity and stably exhibits the gas barrier property.

The details of the vapor deposition method are the same as those described in the section (A) First gas barrier layer, and therefore the description is omitted here. The coating film forming method will be described below.

<Coating film formation method>
The second gas barrier layer according to the present invention is formed by further applying energy to a coating film formed by applying a coating liquid containing an inorganic compound, preferably a coating liquid containing a silicon compound (coating method). It may be formed by a film forming method). By applying this energy, the second gas barrier layer exhibits a gas barrier property. Hereinafter, the coating film forming method will be described by taking a silicon compound as an example of the inorganic compound, but the inorganic compound is not limited to the silicon compound.

(Silicon compound)
The silicon compound is not particularly limited as long as a coating liquid containing the silicon compound can be prepared.

Among them, in terms of film-forming properties, few defects such as cracks, and a small amount of residual organic matter, polysilazanes such as perhydropolysilazane and organopolysilazane; polysiloxanes such as silsesquioxane are preferable, and gas barrier performance is high, Polysilazane is more preferable, and perhydropolysilazane is particularly preferable, because the barrier performance is maintained even when bent and under high temperature and high humidity conditions.

Polysilazane is a polymer having a silicon-nitrogen bond, and SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, and N—H, and a ceramic such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer.

Specifically, polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl)alkyl group. .. In this case, R ₁ , R ₂ and R ₃ may be the same or different. Preferably, R ₁ , R ₂ and R ₃ are hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, phenyl group, vinyl group, 3-(triethoxy group). A silyl)propyl group or a 3-(trimethoxysilylpropyl) group.

In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) may be determined so as to have a number average molecular weight of 150 to 150,000 g/mol. preferable.

In the compound having the structure represented by the general formula (I), one of the preferable embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

Alternatively, the polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _1′ , R _2′ , R _3′ , R _4′ , R _5′ and R _6′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, It is an aryl group, a vinyl group or a (trialkoxysilyl)alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different.

In the general formula (II), n′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined so as to have a number average molecular weight of 150 to 150,000 g/mol. Preferably. Note that n'and p may be the same or different.

Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _1″ , R _2″ , R _3″ , R _4″ , R _5″ , R _6″ , R _7″ , R _8″ and R _9″ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl)alkyl group, wherein R _1″ , R _2″ , R _3″ , R _4″ , R _5″ , R _6″ , R _7″ , R _8″ and R _9″ may be the same or different.

In the general formula (III), n″, p″ and q are integers, and polysilazane having a structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g/mol. Is preferably defined as follows. Note that n″, p″, and q may be the same or different.

In addition, as polysilazane, compounds described in paragraphs “0095” to “0097” of JP-A-2005-003464 and commercial products can be used.

When polysilazane is used, the content of polysilazane in the second gas barrier layer before application of energy may be 100 mass% when the total mass of the second gas barrier layer is 100 mass %. When the second gas barrier layer contains a substance other than polysilazane, the polysilazane content in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. It is more preferable that the amount is 70% by mass or more and 95% by mass or less.

(Coating liquid for forming second gas barrier layer)
Regarding the composition of the second gas barrier layer-forming coating liquid, the coating method, the drying temperature of the coating film obtained after coating, the method of removing water from the coating film, etc., paragraphs “0092” to “JP-A-2015-033764”. The conditions described in “0101” can be appropriately referred to and adopted.

<Applying energy>
Subsequently, energy is applied to the coating film formed as described above to cause a conversion reaction of a silicon compound into silicon oxide, silicon oxynitride, or the like, and the second gas barrier layer develops gas barrier properties. Reforming to a thin inorganic thin film. As the modification treatment, from the viewpoint of adaptation to a plastic substrate, a conversion treatment by a plasma treatment or an ultraviolet irradiation treatment that allows a conversion reaction at a lower temperature is preferable. As a specific method of this conversion reaction, the conditions described in paragraphs “0120” to “0123” and “0130” to “0145” of JP-A-2005-003464 can be appropriately referred to and adopted. ..

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . Within the above range, the modification efficiency will be sufficient and the abrasion of the coating film and the damage to the substrate can be suppressed.

The irradiation energy amount (irradiation amount) of the vacuum ultraviolet ray on the coating film surface is preferably 100 mJ/cm ^{2 to} 50 J/cm ² , more preferably 200 mJ/cm ^{2 to 20} J/cm ² , and 500 mJ/cm 2. More preferably, it is ^{2 to} 10 J/cm ² . Within the above range, the modification is sufficient, and the occurrence of cracks and the thermal deformation of the base material can be suppressed.

Further, the vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as a gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter, also referred to as a carbon-containing gas), a carbon-containing gas may be used alone, but a rare gas or H ₂ is used as a main gas. It is preferable to add a small amount of the contained gas. Examples of the plasma generation method include capacitively coupled plasma.

The second gas barrier layer may be a single layer or a laminated structure of two or more layers. When the second gas barrier layer has a laminated structure of two or more layers, the second gas barrier layers may have the same composition or different compositions. Further, when the second gas barrier layer has a laminated structure of two or more layers, the second gas barrier layer may be composed of only a layer formed by a vapor phase film forming method, or formed by a coating film forming method. It may consist of only a layer, or may be a combination of a layer formed by a vapor phase film forming method and a layer formed by a coating film forming method.

However, it is preferable that the second gas barrier layer is formed by a vapor phase film formation method from the viewpoint that the composition is unlikely to change with humidity and a high gas barrier property can be obtained.

The thickness of the second gas barrier layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 1000 nm, and more preferably 50 to 500 nm. Within this range, a good balance between gas barrier properties and impact resistance is obtained, which is preferable. The thickness of the second gas barrier layer can be measured by TEM observation.

[(D) Third Gas Barrier Layer]
The gas barrier film according to the present invention has (D) a third gas barrier layer (hereinafter, also simply referred to as layer (D)). The layer (D) satisfies the composition range represented by SiO _w N _x (however, 0.20<w≦0.55, 0.66≦x<0.75) and has a thickness of 50 nm or more and 1000 nm or less. Is a layer.

The layer (D) also has a gas barrier property, but is a layer that also functions as a so-called desiccant layer that captures water vapor by reacting with water vapor that has slowly entered. For example, in the order of layer (A)/layer (B)/layer (C)/layer (D), most of the water vapor entering from the layer (A) side up to layer (C). Is a barrier. However, a slight amount of water vapor may intrude from the defective portion of the layer (C). By capturing this water vapor in the layer (D), a higher gas barrier property can be exhibited.

The thickness of the layer (D) is 50 nm or more and 1000 nm or less. When the thickness of the layer (D) is less than 50 nm, the total amount of compounds that react with water vapor as a desiccant becomes small, so that the amount of water vapor that can be captured is also limited and the desiccant function is lost within the useful life required for the device. The barrier property may be reduced. On the other hand, when the thickness exceeds 1000 nm, for example, when the layer (D) is formed by modification by applying energy, the modification may be insufficient and the barrier property may be deteriorated, and the cost may be increased. Further, in the layer including the layer (D), there is a concern that cracks may occur, and the productivity may be reduced.

The thickness of the layer (D) is preferably 100 nm or more and 300 nm or less. Within this range, the effect of maintaining good gas barrier properties and the effect of reducing cost during the service life required for the device are further improved.

The layer (D) may be in the form of one continuous layer or two or more as long as it exists between the layer (C) and the (E) fourth gas barrier layer described later. May be present as a plurality of layers. When two or more layers (D) are present, the sum (total thickness) of the thicknesses of all the layers (D) may be within the above range.

Those skilled in the art can adjust the Si/O/N composition ratio and thickness of the layer (D) by any method. For example, the layer (D) can be formed by forming the gas barrier layer by the coating film forming method described in the section of the (C) second gas barrier layer, but in this case, the coating liquid containing the silicon compound is used. Thickness, degree of drying after coating, amount of energy to be applied (for example, when applying energy by irradiating vacuum ultraviolet rays, adjust illuminance, plasma density, irradiation time, etc.), atmosphere at the time of energy application (especially The oxygen concentration) may be adjusted. In the case of the coating film forming method, oxygen can be reduced in the composition ratio of the layer (D) by reducing the amount of applied energy. Further, when the thickness of the coating liquid containing the silicon compound is increased, the thickness of the layer is increased, and therefore, those skilled in the art can adjust the thickness of the coating film according to the desired thickness of the layer.

The layer (D) can be formed also by a vapor phase film forming method, but when the vapor phase film forming method is adopted, there is a concern that the film forming step becomes complicated and the cost increases. From the viewpoint of cost reduction, a coating film forming method is preferable, and a method in which energy is applied to a coating film obtained by coating and drying a coating liquid containing polysilazane is more preferable.

The details of the type of solvent and the type of polysilazane used in the coating liquid (third gas barrier layer forming coating liquid) used in the coating film forming method, the coating method and the drying method, and the energy applying method are described above. Since it is the same as the content described in the section of the second gas barrier layer, detailed description thereof will be omitted here. The application of energy is preferably performed by vacuum ultraviolet rays from the viewpoint of reforming efficiency (effect of improving gas barrier property with respect to applied energy).

When the layer (D) is formed by a coating film forming method, the thickness of the coating liquid (coating film) after drying is preferably 60 nm or more and 1000 nm or less, more preferably 100 nm or more and 300 nm or less. The solution may be applied. Further, the amount of energy applied is preferably ^{500mJ / cm 2 ~10J / cm 2} , more preferably ^{1J / cm 2 ~8J / cm 2} . Furthermore, the oxygen concentration of the atmosphere at the time of applying energy is preferably 0.001 to 2% by volume, more preferably 0.005 to 1% by volume.

The composition distribution in the thickness direction and the thickness of the layer (D) and the layer (E) described later can be obtained by measurement by a method using XPS (photoelectron spectroscopy) analysis as described below.

Since the etching rates of the layer (D) and the layer (E) according to the present invention differ depending on the composition, in the present invention, the thickness in XPS analysis is once determined based on the etching rate in terms of SiO ₂ . Based on the cross-sectional TEM image of the same sample, the interface between each layer of the layers formed by stacking was specified to determine the thickness per layer, and this was compared with the composition distribution in the thickness direction determined by XPS analysis. However, each layer in the composition distribution in the thickness direction is specified, and each layer obtained from the XPS analysis is matched so that the thickness of each layer obtained from the XPS analysis corresponding to each layer matches the thickness of each layer obtained from the cross-sectional TEM image. The thickness is corrected by uniformly multiplying the thickness by the coefficient.

The XPS analysis in the present invention was carried out under the following conditions, but even if the apparatus and the measurement conditions are changed, a measuring method in accordance with the gist of the present invention can be applied without any problem.

The measurement method in accordance with the gist of the present invention is mainly the resolution in the thickness direction, and the etching depth per measurement point (corresponding to the following conditions of sputter ion and depth profile) is 1 to 15 nm. The thickness is preferably 1 to 10 nm, and more preferably 1 to 10 nm.

<< XPS analysis conditions >>
・Device: QUANTERASXM made by ULVAC-PHI
・X-ray source: Monochromatic Al-Kα
・Measurement area: Si2p, C1s, N1s, O1s
・Sputtering ion: Ar (2 keV)
・Depth profile: Repeat measurement after sputtering for a certain period of time. A single measurement is in terms of SiO _2, - adjusting a sputtering time so that the thickness of about 2.8nm Quantification sought background Shirley method, the relative sensitivity coefficient method from the peak area obtained with Used to quantify. MultiPak manufactured by ULVAC-PHI, Inc. is used for data processing.

In this way, primary data of the profile of the composition distribution of the gas barrier layer in the film thickness direction is obtained.

In addition, the cross section of each sample is photographed by TEM to determine each film thickness of the laminated structure. The profile of the composition distribution in the film thickness direction obtained above is corrected using the actual film thickness data obtained from the TEM image to obtain the composition distribution in the film thickness direction of the layer. Based on this, the thicknesses of the layer (D) and the layer (E) are obtained.

As a method of obtaining the thickness per layer from a TEM image, a gas barrier film may be prepared into a thin piece by the following FIB processing apparatus, and then a cross-sectional TEM observation may be performed according to a standard method. In this way, the thickness of each layer can be calculated. An example that can be used for FIB processing and TEM observation is shown below.

<< FIB processing >>
-Device: SII SMI2050
・Processing ion: (Ga 30kV)
-Sample thickness: 100 nm to 200 nm
<<TEM observation>>
-Device: JEM2000FX (accelerating voltage: 200 kV) manufactured by JEOL Ltd.

[(E) Fourth Gas Barrier Layer]
The gas barrier film according to the present invention has (E) a fourth gas barrier layer (hereinafter, also simply referred to as a layer (E)). The layer (E) satisfies the composition range represented by SiO _y N _z (where 0.55<y≦2.0 and 0.25<z≦0.66) and has a thickness of 8 nm or more and 200 nm or less. Is a layer.

Layer (E) has a very high gas barrier property. Since the layer (E) has a lower reactivity with water vapor than the layer (D) and the composition change is small even under high temperature and high humidity, it is possible to maintain a very high gas barrier property for a long period of time. The layers (A)/layers (B)/layers (C)/layers (D)/layers (E) are arranged in this order, and water vapor that could not be trapped in the layers (D) is almost completely barriered in the layers (E). It This makes it possible to prevent water vapor from entering the electronic device body provided directly on the layer (E), and to suppress, for example, dark spots from occurring in the organic EL element.

The thickness of the layer (E) is 8 nm or more and 200 nm or less. If the thickness of the layer (E) is less than 8 nm, the water vapor may not be sufficiently blocked. On the other hand, when the thickness exceeds 200 nm, the improvement in gas barrier property accompanying the increase in film thickness saturates, and the productivity also decreases, so that no cost advantage can be obtained.

The thickness of the layer (E) is preferably 20 nm or more and 150 nm or less. Within this range, good gas barrier properties can be maintained for the useful life required of the device, and for example, the generation of dark spots when used in an organic EL element can be suppressed, and the growth of dark spots can be prevented even if they occur. The effect that can be suppressed is further improved.

The layer (E) may be in the form of being present as one continuous layer as long as it is present between the layer (D) and the electronic device body, or is present as two or more layers. It may be in the form. When there are two or more layers (E), the sum (total thickness) of the thicknesses of all the layers (E) may be within the above range.

Those skilled in the art can adjust the Si/O/N composition ratio and the thickness of the layer (E) by any method. For example, the layer (E) can be formed by forming the gas barrier layer by the coating film forming method described in the section (C) Second gas barrier layer, but in this case, a coating liquid containing a silicon compound is used. Thickness, degree of drying after coating, amount of energy to be applied (for example, when applying energy by irradiating vacuum ultraviolet rays, illuminance, plasma density, irradiation time, etc. are adjusted), atmosphere at the time of energy application ( In particular, the oxygen concentration) may be adjusted. In the case of the coating film forming method, by increasing the amount of energy applied, oxygen can be increased in the composition ratio of the layer (E). Further, when the thickness of the coating liquid containing the silicon compound is increased, the thickness of the layer is increased, and therefore, those skilled in the art can adjust the thickness of the coating film according to the desired thickness of the layer.

The layer (E) can be formed also by a vapor phase film forming method, but when the vapor phase film forming method is adopted, there is a concern that the cost increases due to the complicated film forming process. From the viewpoint of cost reduction, a coating film forming method is preferable, and a method in which energy is applied to a coating film obtained by coating and drying a coating liquid containing polysilazane is more preferable.

The details of the type of solvent and the type of polysilazane used in the coating liquid used for the coating film forming method (the coating liquid for forming the fourth gas barrier layer), the coating method and the drying method, and the method of applying energy are described above. Since it is the same as the content described in the section of the second gas barrier layer, detailed description thereof will be omitted here. The application of energy is preferably performed by vacuum ultraviolet rays from the viewpoint of reforming efficiency (effect of improving gas barrier property with respect to applied energy).

When the layer (E) is formed by a coating film forming method, the thickness of the coating liquid (coating film) after drying is preferably 10 nm or more and 200 nm or less, more preferably 20 nm or more and 150 nm or less. The solution may be applied. Further, the amount of energy applied is preferably ^{500mJ / cm 2 ~10J / cm 2} , more preferably ^{1J / cm 2 ~8J / cm 2} . The oxygen concentration in the atmosphere when energy is applied is preferably 0.02 to 2% by volume, more preferably 0.05 to 1% by volume.

The composition distribution and the thickness of the layer (E) in the thickness direction can be obtained by measurement by the method using the XPS (photoelectron spectroscopy) analysis as described above.

[Layer having various functions]
The gas barrier film according to the present invention may be provided with layers having various functions.

(Anchor coat layer)
An anchor coat layer is formed on the surface of the buffer layer on the side where the gas barrier layer (first gas barrier layer, second gas barrier layer) according to the present invention is formed, for the purpose of improving adhesion with the gas barrier layer. Good.

As the anchor coating agent used in the anchor coating layer, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate are used alone. Or in combination of two or more.

Conventionally known additives may be added to these anchor coating agents. Then, the above anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent and the like. be able to. The coating amount of the above anchor coating agent is preferably about 0.1 to 5.0 g/m ² (dry state).

The anchor coat layer can also be formed by a vapor phase method such as a physical vapor deposition method or a chemical vapor deposition method. For example, as described in Japanese Unexamined Patent Application Publication No. 2008-142941, an inorganic film mainly containing silicon oxide can be formed for the purpose of improving the adhesiveness and the like. Alternatively, by forming an anchor coat layer as described in JP-A-2004-314626, when forming an inorganic thin film thereon by a vapor phase method, a gas generated from the base material side is blocked to some extent. Then, the anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
The gas barrier film according to the present invention may have a smooth layer between the buffer layer and the first gas barrier layer or between the buffer layer and the second gas barrier layer. The smooth layer used in the present invention flattens the rough surface of the resin base material having projections or the like, or fills the irregularities or pinholes generated in the transparent inorganic compound layer by the projections present on the resin base material to flatten it. It is provided for. Such a smooth layer is basically prepared by curing a photosensitive material or a thermosetting material.

As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include resin compositions in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate is dissolved. Specifically, UV curing type organic/inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use any mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule may be used. There is no particular limitation.

Specific examples of thermosetting materials include Tuttprom series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat Co., Ltd., Nanohybrid silicone manufactured by ADEKA CORPORATION, and Unidick manufactured by DIC Corporation. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic/organic nanocomposite material SSG manufactured by Nitto Boseki Co., Ltd. Examples thereof include a coat, a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

The method for forming the smooth layer is not particularly limited, but it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber and a plasticizer can be added to the above-mentioned photosensitive resin, if necessary. Further, regardless of the stacking position of the smooth layer, an appropriate resin or additive may be used in any of the smooth layers in order to improve the film-forming property and prevent the occurrence of pinholes in the film.

The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 μm to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

The smoothness of the smooth layer is a value expressed by the surface roughness defined by JIS B 0601:2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. Within this range, the coatability is impaired even when the barrier layer is applied by a coating method or by a coating method such as a wire bar or a wireless bar even when the coating means comes into contact with the smooth layer surface. In addition, it is easy to smooth the unevenness after coating.

(Protective layer)
The gas barrier film according to the present invention preferably has a protective layer on the surface of the first gas barrier layer opposite to the surface having the buffer layer. By having the protective layer, the electronic device of the present invention has higher durability (long-term reliability). Further, the protective layer may have a function of preventing scratches on the surface of the electronic device.

As a material for forming the protective layer, a hard coat such as a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule or a monovalent unsaturated organic compound having one polymerizable unsaturated group in the molecule An agent can be mentioned.

As another additive, 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. ..

Further, the protective layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, etc. as other components of the hard coating agent and the matting agent.

The protective layer as described above is prepared as a coating solution by adding a hard coating agent, a matting agent and, if necessary, other components, and optionally using a diluent solvent, and the coating solution is used as a support film. It can be formed by coating the surface with a conventionally known coating method and then irradiating it with ionizing radiation to cure it.

As a method of irradiating with ionizing radiation, irradiation with ultraviolet rays in a wavelength range 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, or scanning is performed. It can be performed by irradiating an electron beam in a wavelength region of 100 nm or less emitted from an electron beam accelerator of curtain type or curtain type.

The thickness of the protective layer is preferably in the range of 50 to 5000 nm, more preferably 100 to 2000 nm.

(Side sealing)
As described above, in order to prevent the permeation of water from the edge of the layer (B) according to the present invention, the sealing for shutting off the outside air so as to surround the outer periphery of the electronic device of the present invention. Material may be provided. Examples of such a sealing material include a film containing silicon oxide, nitride, and/or oxynitride as a main component described in JP-A No. 11-144864, and JP-A No. 2003-243155. Examples thereof include a film containing a metal oxide or a metal nitride.

In addition, a sealing member such as a metal foil such as an aluminum foil or a copper foil, a laminate of an inorganic layer and an organic layer, or the like may be provided so as to cover the entire electronic device.

[Method of manufacturing electronic device]
The electronic device of the present invention is not particularly limited, but is preferably obtained by the following manufacturing method.

(1) A step of forming a first gas barrier layer on one surface of a resin base material to be a buffer layer, and the step of forming the first gas barrier layer on the surface of the resin base material opposite to the surface on which the first gas barrier layer is formed. A step of forming a second gas barrier layer, a third gas barrier layer, and a fourth gas barrier layer in this order from the resin substrate side to obtain a gas barrier film; and a step of forming an electronic device body on the fourth gas barrier layer. And a manufacturing method including.

(2) A step of forming a second gas barrier layer, a third gas barrier layer, and a fourth gas barrier layer in this order from the resin base material side on one surface of the resin base material to be a buffer layer, and the resin base material. A step of forming a first gas barrier layer on the surface opposite to the surface on which the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer are formed to obtain a gas barrier film; Forming an electronic device body on the fourth gas barrier layer.

(3) A step of forming a second gas barrier layer, a third gas barrier layer, and a fourth gas barrier layer in order from the resin base material side on one surface of the resin base material to be a buffer layer; A step of forming an electronic device body on the gas barrier layer, and a surface of the resin substrate on which the second gas barrier layer, the third gas barrier layer, the fourth gas barrier layer, and the electronic device body are formed. Forming a first gas barrier layer on the surface opposite to the above.

(4) A step of forming the first gas barrier layer on one surface of the first resin base material to obtain a first barrier film, and the second resin on one surface of the second resin base material. Forming a second barrier film by forming the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer in order from the base material side; and using an adhesive or a pressure-sensitive adhesive, A surface of the first barrier film on which the first gas barrier layer is formed, and the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer of the second barrier film are formed. And a step of bonding the surface opposite to the above described side, and a step of forming the electronic device body on the fourth gas barrier layer.

(5) A step of forming the first gas barrier layer on one surface of the first resin substrate to obtain a first barrier film, and the second resin on one surface of the second resin substrate. Forming the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer in this order from the base material side to obtain a second barrier film; and the step of forming the second barrier film No. 4, a step of forming the electronic device body on the gas barrier layer, a surface of the first barrier film on which the first gas barrier layer is formed using an adhesive or a pressure-sensitive adhesive, and the second barrier. Bonding the second gas barrier layer, the third gas barrier layer, the fourth gas barrier layer, and the surface of the conductive film opposite to the side on which the electronic device body is formed. Method.

Among these, the electronic device obtained by the manufacturing method of (2), (3) or (5) is preferable, and the electronic device obtained by the manufacturing method of (3) or (5) is more preferable. This is because peeling of the first gas barrier layer that may occur in the process of forming the electronic device body can be prevented.

In addition, in the electronic device obtained by the manufacturing method of (4) or (5), the first resin base material is provided outside the first gas barrier layer (side closer to the outside air). Such embodiments are also within the scope of the electronic device of the present invention.

Since the method of forming the layers (A) to (E) is as described above, the description thereof is omitted here.

[Absorptance of light with wavelength of 450 nm]
The gas barrier film according to the present invention preferably has an absorptance of light having a wavelength of 450 nm (hereinafter, also simply referred to as an absorptance at 450 nm) of less than 15%. By using the gas barrier film according to the present invention having a low absorptance of light having a wavelength of 450 nm (that is, having high transmittance) for a display device, a wavelength of 450 nm relating to blue light in the process of reaching visible light from a light source to a user. Absorption of nearby light by the gas barrier film can be suppressed as much as possible.

By having the layer (D) and the layer (E), the absorptance at 450 nm of the gas barrier film according to the present invention can be lowered. In the gas barrier film according to the present invention, the absorptance at 450 nm is preferably less than 15%, more preferably less than 10%, further preferably less than 8%. The lower limit of the absorptance at 450 nm is not particularly limited, but is, for example, substantially 0% or more.

The absorptance at 450 nm can be measured by a spectrophotometer or a spectrocolorimeter. The absorptance at 450 nm is obtained by measuring the transmittance A (%) and the reflectance B (%) at 450 nm using, for example, a spectrocolorimeter (for example, CM-3600d, manufactured by Konica Minolta Co., Ltd.), and Can be obtained using.

Further, the gas barrier film according to the present invention preferably has a transmittance in the visible light region (400 to 700 nm) of 80% or more, more preferably 83% or more. When the transmittance in the visible light region (400 to 700 nm) is 80% or more, a gas barrier film having excellent optical properties in the entire visible light region is provided. The total light transmittance in the visible light region is measured according to JIS K7375:2008.

[Electronic device body]
The electronic device of the present invention can be preferably applied to a device whose performance deteriorates due to chemical components in the air (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.).

Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effect of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples.

[Resin base material]
Substrate A: A PET film with a double-sided hard coat (total thickness: 136 μm, PET thickness: 125 μm, manufactured by Kimoto Co., Ltd., trade name: KB film (trademark) 125G1SBF) was used.

Substrate A: A PET film with a double-sided hard coat (total thickness: 58 μm, PET thickness: 50 μm, manufactured by Kimoto Co., Ltd., trade name: KB film (trademark) 50G1SBF) was used.

[Formation of gas barrier layer by vapor deposition method]
Roll-to-roll type CVD of a type (having a first film forming unit and a second film forming unit) in which two apparatuses having a film forming unit composed of opposed film forming rolls described in Japanese Patent No. 4268195 are connected. A film forming apparatus was used (see FIG. 2). The effective film-forming width is 1000 mm, and the film-forming conditions are as follows: transport speed, supply amount of source gas (HMDSO) of each of the first film forming unit and the second film forming unit, supply amount of oxygen gas, degree of vacuum, applied power, The frequency of the power source and the number of film formations (number of passes of the apparatus) were adjusted. In contrast to the first pass, the substrate is conveyed in the unwinding direction in the second pass, but even if the pass direction is different, the film forming unit that first passes through the first film forming unit The film portion was used as the second film forming portion.

As other conditions, the power supply frequency was 84 kHz and the film-forming roll temperatures were all 30°C. The base material used was one in which a heat-resistant protective film was attached to the surface opposite to the film-forming surface and wound up. When forming a film on both sides, a heat-resistant protective film is further attached to the film-formed surface of the substrate after film formation on one side, and then the protective film on the opposite surface, which is the next film-forming surface, is peeled off. A wound one was used. The film thickness was determined by cross-sectional TEM observation.

The film forming conditions of the first film forming section and the second film forming section are shown in Table 1 below.

[Formation of Third Gas Barrier Layer and Fourth Gas Barrier Layer]
The third gas barrier layer and the fourth gas barrier layer were formed by applying a coating solution as shown below to form a coating film and then performing modification by vacuum ultraviolet irradiation to obtain a gas barrier layer.

A dibutyl ether solution containing 20% by mass of perhydropolysilazane (NN120-20, manufactured by AZ Electronic Materials) and an amine catalyst (N,N,N',N'-tetramethyl-1,6-diaminohexane (TMDAH). )) perhydropolysilazane 20% by mass dibutyl ether solution (AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4:1 (mass ratio), and further for adjusting the dry film thickness. A coating solution was prepared by appropriately diluting with dibutyl ether.

The base material on which the gas barrier layer was formed, or the above-mentioned base material was cut out into a sheet and prepared. The layer formation by coating was performed on the already formed gas barrier layer surface or the smooth surface of the substrate. The coating solution was applied by a spin coating method so as to have a dry film thickness shown in Table 2 below, and dried at 80° C. for 2 minutes. Then, using a Xe excimer lamp having a wavelength of 172 nm, the dried coating film was subjected to vacuum ultraviolet irradiation treatment under the conditions of oxygen concentration and irradiation energy shown in Table 2 below, and the third gas barrier layer and the fourth gas barrier layer were formed. A gas barrier layer was formed.

The irradiation conditions of vacuum ultraviolet rays are shown in Table 2 below.

The composition distributions in the thickness direction of the third gas barrier layer and the fourth gas barrier layer were measured and obtained by the method using XPS analysis as described below.

(XPS analysis conditions)
・Device: QUANTERASXM made by ULVAC-PHI
・X-ray source: Monochromatic Al-Kα
・Measurement area: Si2p, C1s, N1s, O1s
・Sputtering ion: Ar (2 keV)
・Depth profile: Repeat measurement after sputtering for a certain period of time. In one measurement, the sputtering time was adjusted so that the thickness was about 2.8 nm in terms of SiO _2. Quantitative: The background was obtained by the Shirley method, and the relative sensitivity coefficient method was used from the obtained peak area. Was quantified. For data processing, MultiPak manufactured by ULVAC-PHI, Inc. was used.

In this way, primary data of the profile of the composition distribution in the film thickness direction of the third gas barrier layer and the fourth gas barrier layer was obtained. The obtained profile of the composition distribution in the film thickness direction is corrected by using the actual film thickness data obtained from the TEM image to obtain the composition distribution in the film thickness direction, and the third gas barrier layer and the fourth gas barrier layer I asked for the thickness.

With respect to the first gas barrier layer, the buffer layer, and the second gas barrier layer, cross sections were photographed by TEM to determine the film thickness.

(Comparative Example 1)
A 0.7 mm thick glass plate was prepared.

(Comparative example 2)
A thin film glass having a thickness of 35 μm was prepared.

(Comparative example 3)
A composite film was prepared by adhering a thin film glass having a thickness of 35 μm on a PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc., product name: Lumirror (registered trademark) 50U48).

(Comparative example 4)
A second gas barrier layer was formed on one surface of the substrate A under the above condition V3. Next, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P3 and P1 described above, a third gas barrier layer and a fourth gas barrier layer were provided, and a gas barrier film was produced.

(Example 1)
A first gas barrier layer was formed on one surface of the substrate A under the above condition V1. Then, a second gas barrier layer was formed on the surface of the substrate A opposite to the side on which the first gas barrier layer was formed under the above condition V2. Next, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P3 and P1 described above, a third gas barrier layer and a fourth gas barrier layer were provided, and a gas barrier film was produced.

(Example 2)
A first gas barrier layer was formed on one surface of the substrate A under the above condition V2. Then, a second gas barrier layer was formed on the surface of the substrate A opposite to the side on which the first gas barrier layer was formed under the above condition V3. Next, a gas barrier layer was formed on the second gas barrier layer under the above condition P3, a third gas barrier layer and a fourth gas barrier layer were provided, and a gas barrier film was produced.

(Example 3)
A first gas barrier layer was formed on one surface of the substrate A under the above condition V1. Then, a second gas barrier layer was formed on the surface of the substrate A opposite to the side on which the first gas barrier layer was formed under the above condition V3. Then, a gas barrier layer is sequentially formed on the second gas barrier layer under the conditions of P3, P3, and P1 described above, and a third gas barrier layer and a fourth gas barrier layer are provided to provide a gas barrier property. A film was made.

(Example 4)
A first gas barrier layer was formed on one surface of the substrate A under the above condition V1. Then, on the first gas barrier layer, a UV curing type hard coat layer was formed with a thickness of 15 μm. Further, a second gas barrier layer was formed on the hard coat layer under the above condition V3. Next, a gas barrier layer was sequentially formed under the conditions of P3 and P1 described above, a third gas barrier layer and a fourth gas barrier layer were provided, and a gas barrier film was produced.

The UV-curable hard coat layer was formed as follows. That is, UV curable resin Opstar (registered trademark) Z7527 manufactured by JSR Corporation was applied with an applicator so that the dry film thickness was 15 μm, and then dried at 80° C. for 10 minutes. Then, it was cured under air with a high-pressure mercury lamp at an irradiation energy amount of ² J/cm ² to form a hard coat layer.

(Comparative example 5)
A gas barrier film was produced in the same manner as in Example 4 except that the hard coat layer had a thickness of 6 μm.

(Example 5)
A barrier film 1 having a first gas barrier layer formed on one surface of the substrate A under the above condition V1 was prepared. On the first gas barrier layer of this barrier film 1, the surface of the gas barrier film obtained by the same method as in Comparative Example 1 on which the gas barrier layer was not formed was covered with a transparent adhesive (Sekisui Chemical Co., Ltd., A highly transparent double-sided tape 5402, 25 μm thick) was used for bonding to prepare a gas barrier film.

(Example 6)
A second gas barrier layer was formed on one surface of the substrate A under the above P3 condition. Next, a gas barrier layer was prepared by sequentially forming a gas barrier layer on the second gas barrier layer under the above conditions P3 and P1 to provide a third gas barrier layer and a fourth gas barrier layer. Separately, a barrier film 1 having a first gas barrier layer formed on one surface of the substrate A under the above condition V1 was prepared. For the first gas barrier layer of the barrier film 1 and the surface of the barrier film 2 on which the gas barrier layer is not formed, a transparent adhesive (manufactured by Sekisui Chemical Co., Ltd., highly transparent double-sided tape 5402, 25 μm thick) is used. And laminated to prepare a gas barrier film.

(Comparative example 6)
A barrier film 1 having a first gas barrier layer formed on one surface of the substrate A under the above condition V1 was prepared. The surface of the barrier film 1 on which the first gas barrier layer is not formed and the surface of the gas barrier film obtained by the same method as Comparative Example 4 on which the gas barrier layer is not formed are transparent adhesive (Sekisui A highly transparent double-sided tape 5402 manufactured by Kagaku Kogyo Co., Ltd., having a thickness of 25 μm) was used for bonding to prepare a gas barrier film.

(Example 7)
A barrier film 1 was prepared in which a first gas barrier layer was formed by sputtering on the one surface of the base material B under the condition of V4. On the first gas barrier layer of the barrier film 1, the surface of the gas barrier film obtained by the same method as in Comparative Example 4 on which the gas barrier layer was not formed was transparent adhesive (manufactured by Sekisui Chemical Co., Ltd., highly transparent). A double-sided tape 5402 having a thickness of 25 μm) was used for bonding to prepare a gas barrier film.

(Comparative Example 7)
A second gas barrier layer was formed on one surface of the substrate A under the above condition V3. Then, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P2 and P1 described above, a third gas barrier layer and a fourth gas barrier layer were provided, and a barrier film 2 was produced. ..

A gas barrier film was produced in the same manner as in Example 5 except that the above barrier film 2 was used instead of the gas barrier film obtained by the same method as in Comparative Example 1.

(Comparative Example 8)
A second gas barrier layer was formed on one surface of the substrate A under the above condition V3. Next, a gas barrier layer was formed on the second gas barrier layer under the above condition P4, a third gas barrier layer was provided, and a barrier film 2 was produced.

A gas barrier film was produced in the same manner as in Example 5 except that the above barrier film 2 was used instead of the gas barrier film obtained by the same method as in Comparative Example 1.

(Comparative Example 9)
A gas barrier layer was formed on both surfaces of the substrate A under the above condition V3 to prepare a gas barrier film.

(Example 8)
A hard coat layer serving as a protective layer having a thickness of 500 nm was formed on the surface of the first gas barrier layer of the gas barrier film obtained in Example 3 to prepare a gas barrier film.

The protective layer was formed as follows. That is, UV curable resin Opstar (registered trademark) Z7527 manufactured by JSR Co., Ltd. was applied with an applicator so that the dry film thickness was 500 nm, and then dried at 80° C. for 3 minutes. Then, it was cured under air with a high pressure mercury lamp at an irradiation energy amount of 0.5 J/cm ² to form a protective layer.

(Comparative Example 10)
An organic EL device described later was formed on the first gas barrier layer of the gas barrier film obtained in Example 3.

(Comparative Example 11)
A gas barrier film having a gas barrier layer formed on one surface of the substrate A under the above condition V1 was prepared. The surface of this film on which no gas barrier layer was formed and the surface of the fourth gas barrier layer of the gas barrier film obtained by the same method as in Comparative Example 4 were treated with a transparent adhesive (manufactured by Sekisui Chemical Co., Ltd. A transparent double-sided tape 5402, 25 μm thick) was used for lamination to prepare a gas barrier film.

(Example 9)
A second gas barrier layer was formed on one surface of the substrate A under the above P3 condition. Then, a gas barrier layer was sequentially formed on the second gas barrier layer under the above conditions P3 and P1 to prepare a barrier film 2 provided with a third gas barrier layer and a fourth gas barrier layer. .. Further, an organic EL element described later was formed on the fourth gas barrier layer of the barrier film 2.

Separately, a barrier film 1 having a first gas barrier layer formed on one surface of the substrate A under the above condition V1 was prepared. A transparent pressure-sensitive adhesive (manufactured by Sekisui Chemical Co., Ltd., highly transparent double-sided tape 5402, 25 μm thick) was used for the first gas barrier layer of the barrier film 1 and the surface of the barrier film 2 on which the organic EL element was not formed. It stuck using and the electronic device was produced.

(Example 10)
An organic EL device described later was formed on the fourth gas barrier layer of the gas barrier film obtained by the same method as in Comparative Example 4. After forming the organic EL element, a gas barrier layer was formed on the surface of the gas barrier film on which the organic EL element was not formed under the conditions of the above V4 to manufacture an electronic device.

Table 3 below shows the constitution of each layer obtained in Examples and Comparative Examples.

<<Method of manufacturing organic EL device>>
Using the glass plate prepared in Comparative Examples 1-2, the composite film prepared in Comparative Example 3, and the gas barrier films obtained in Examples 1-8 and Comparative Examples 4-11, by the method as shown below, A bottom emission type organic electroluminescence element (organic EL element) was prepared so that the area of the light emitting region was 5 cm×5 cm. Although a method for producing an organic EL element using a gas barrier film is shown below, an organic EL element was produced by a similar method for a glass plate and a composite film.

(Formation of underlying layer and first electrode)
The gas barrier film was fixed to a substrate holder of a commercially available vacuum vapor deposition apparatus, the compound 118 was put into a resistance heating boat made of tungsten, and the substrate holder and the heating boat were attached to the first vacuum tank of the vacuum vapor deposition apparatus. It was In addition, silver (Ag) was put into a resistance heating boat made of tungsten and attached to the second vacuum tank of the vacuum vapor deposition apparatus.

Next, after depressurizing the first vacuum tank of the vacuum vapor deposition apparatus to 4×10 ⁻⁴ Pa, the heating boat containing the compound 118 is energized and heated, and the vapor deposition rate is 0.1 nm/sec to 0.2 nm/sec. Then, the underlayer of the first electrode was provided to have a thickness of 10 nm.

Next, the base material on which the base layer was formed was transferred to a second vacuum tank while keeping the vacuum, the pressure in the second vacuum tank was reduced to 4×10 ⁻⁴ Pa, and then a heating boat containing silver was energized and heated. Thus, the first electrode made of silver and having a thickness of 8 nm was formed at a vapor deposition rate of 0.1 nm/sec to 0.2 nm/sec.

(Organic functional layer to second electrode)
Subsequently, the pressure was reduced to 1×10 ⁻⁴ Pa in vacuum using a commercially available vacuum vapor deposition device, and then the compound HT-1 was vapor-deposited at a vapor deposition rate of 0.1 nm/sec while moving the base material to obtain a 20 nm hole. A transport layer (HTL) was provided.

Next, the compound A-3 (blue light emitting dopant), the compound A-1 (green light emitting dopant), the compound A-2 (red light emitting dopant) and the compound H-1 (host compound), the compound A-3 being the film thickness. In contrast, the deposition rate was changed linearly from 35% by mass to 5% by mass, and the concentrations of Compound A-1 and Compound A-2 were 0.2% by mass independently of the film thickness. As described above, at a vapor deposition rate of 0.0002 nm/sec, the compound H-1 was co-evaporated to have a thickness of 70 nm by varying the vapor deposition rate from 64.6% by mass to 94.6% by mass. Then, a light emitting layer was formed.

Then, the compound ET-1 was vapor-deposited to a film thickness of 30 nm to form an electron transport layer, and further potassium fluoride (KF) was formed to a thickness of 2 nm. Further, 110 nm of aluminum was vapor-deposited to form a second electrode.

The above compound 118, compound HT-1, compound A-1 to 3, compound H-1, and compound ET-1 are the compounds shown below.

(Solid sealing)
Next, an aluminum foil having a thickness of 25 μm was used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) having a thickness of 20 μm was attached as a sealing resin layer to one surface of the aluminum foil. Using the stop member, the samples up to the second electrode were overlaid. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead electrodes of the first electrode and the second electrode were exposed.

Then, the sample was placed in a depressurizing apparatus, and the superposed base material and the sealing member were pressed and held for 5 minutes under a depressurized condition of 0.1 MPa at 90°C. Subsequently, the sample was returned to the atmospheric pressure environment and further heated at 120° C. for 30 minutes to cure the adhesive.

The above-mentioned sealing step is under atmospheric pressure, in a nitrogen atmosphere having a water content of 1 ppm or less, in accordance with JIS B 9920:2002, the measured cleanliness is class 100, the dew point temperature is −80° C. or less, and the oxygen concentration is 0. It was carried out at an atmospheric pressure of 8 ppm or less. It should be noted that the description regarding the formation of the lead wiring from the anode and the cathode is omitted.

In this manner, four electronic devices each having a light emitting region of 5 cm×5 cm were manufactured for one level.

(Absorptance at 450 nm)
Using a spectrophotometer (CM-3600d, manufactured by Konica Minolta Co., Ltd.), the transmittance A (%) and the reflectance B (%) of the gas barrier film (or glass or composite film) at a wavelength of 450 nm are measured, The absorptance (%) at a wavelength of 450 nm was determined by the following formula.

In addition, Example 9 is an estimated value based on Example 6, and Example 10 is an estimated value based on Example 7.

(Dark spot (DS) evaluation)
The organic EL element obtained as described above is energized for 300 hours in an environment of 85° C. and 85% RH, and the number of dark spots having a circle-converted diameter of 200 μm or more is calculated for dark spots that have been generated. The average of four devices was used.

(Impact resistance evaluation)
The organic EL device obtained as described above is placed on a horizontal table with the light emitting surface side up (a flat plate member of a specific material is placed below it), and a steel ball with a diameter of 10 mm is placed on it with a height of 1 m. It was dropped from the position, and the damage status of the device was visually confirmed. In addition, the presence or absence of subsequent light emission was also confirmed.

The above evaluation results are shown in Table 4 below.

As is clear from Table 4 above, the electronic device of the present invention has excellent durability in a high temperature and high humidity environment and excellent impact resistance.

This application is based on Japanese Patent Application No. 2014-56840 filed on Mar. 19, 2014, the disclosure content of which is incorporated by reference in its entirety.

Claims (5)

(A) First gas barrier layer containing a silicon compound:
(B) a buffer layer containing a resin and having a thickness of 10 to 200 μm;
(C) a second gas barrier layer containing a silicon compound and having a thickness of 200 to 1000 nm;
(D) SiO _w N _x (wherein 0.2<w≦0.55, 0.66<x≦0.75) satisfying the composition range and having a thickness of 50 to 1000 nm 3 gas barrier layers;
(E) SiO _y N _z (wherein 0.55<y≦2.0, 0.25<z≦0.66) which satisfies the composition range and has a thickness of 8 to 50 nm. 4 gas barrier layer;
Including a gas barrier film in this order,
An electronic device body formed on the surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer;
An electronic device including :
The electronic device is
Forming a first gas barrier layer on one surface of a first resin substrate to obtain a first barrier film;
The second gas barrier layer is formed by sequentially forming the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer on one surface of the second resin substrate from the second resin substrate side. A step of obtaining a film,
Forming the electronic device body on the fourth gas barrier layer of the second barrier film;
A surface of the first barrier film on which the first gas barrier layer is formed using an adhesive or a pressure-sensitive adhesive, the second gas barrier layer of the second barrier film, and the third gas barrier layer. Bonding the fourth gas barrier layer and the surface opposite to the side on which the electronic device body is formed,
An electronic device obtained by a manufacturing method including. The first gas barrier layer and the second gas barrier layer are formed by a vapor deposition method, and the third gas barrier layer and the fourth gas barrier layer are formed by applying and drying a coating solution containing polysilazane. The electronic device according to claim 1, which is formed by applying energy to the obtained coating film. The electronic device according to claim 2, wherein the application of the energy is performed by irradiating vacuum ultraviolet rays. The electronic device according to claim 1, wherein the gas barrier film has an absorption rate of light having a wavelength of 450 nm of less than 15%. The electronic device according to claim 1, further comprising a protective layer on the surface of the first gas barrier layer opposite to the surface having the buffer layer.