WO2015141741A1 - Electronic device - Google Patents

Abstract

Provided is an electronic device having excellent durability in high-temperature, high-humidity environments and having excellent shock resistance. The electronic device includes a gas-barrier film and an electronic device main body. The gas-barrier film includes, in order: a first gas-barrier layer (A) including an inorganic compound; a buffer layer (B) including resin and having a thickness of 10-200 µm; a second gas-barrier layer (C) including an inorganic compound; a third gas-barrier layer (D) fulfilling a composition range indicated by SiO_wN_x (0.2 < w ≤ 0.55 and 0.66 < x ≤ 0.75) and having a thickness of 50-1,000 nm; and a fourth gas-barrier layer (E) fulfilling a composition range indicated by SiO_yN_z (0.55 < y ≤ 2.0 and 0.25 < z ≤ 0.66) and having a thickness of 8-200 nm. The electronic device main body is formed on the surface of the fourth gas-barrier layer on the opposite side thereof to the third gas-barrier layer.

Description

Electronic devices

The present invention relates to an electronic device.

Conventionally, a gas barrier film formed by laminating a plurality of 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 is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like.

In addition to packaging applications, gas barrier films are required to be developed into 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 gas barrier property at the glass substrate level and a property that does not break (impact resistance).

As a method for forming a gas barrier film, JP 2013-61507 A proposes a method of bonding a plurality of gas barrier films and a method of forming a gas barrier layer on both surfaces of a substrate.

Japanese Patent Application Laid-Open No. 2013-241023 (corresponding to US Patent Application Publication No. 2011/039097) describes a gas barrier including a flexible film-like thin film glass substrate and a composite substrate of thin film glass and a resin film. Sex films have been proposed.

However, the gas barrier film described in JP-A-2013-61507 has a high gas barrier that suppresses the occurrence of dark spots in organic EL elements under high temperature and high humidity conditions such as 85 ° C. and 85% RH. There was a problem of not getting the sex. In addition, the gas barrier film described in Japanese Patent Application Laid-Open No. 2013-241023 (corresponding to US Patent Application Publication No. 2011/039097) has a problem of being easily broken and inferior in impact resistance.

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

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

That is, the present invention provides (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) No. 1 which satisfies the composition range represented by SiO _w N _x (where 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) and has a thickness of 50 to 1000 nm. 3 (E) SiO _y N _z (where 0.55 <y ≦ 2.0, 0.25 <z ≦ 0.66) and a composition range of 8 to 200 nm A gas barrier film including a fourth gas barrier layer having a thickness in this order; and an electronic device body formed on a surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer. And an electronic device.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the film-forming apparatus which can be utilized suitably in order to manufacture the 1st gas barrier layer of the gas barrier film which concerns on this invention, and a 2nd gas barrier layer, 1 is a base material 10 is a delivery roll, 11, 12, 13, and 14 are transport rolls, 15 is a first film forming roll, 16 is a second film forming roll, and 17 is a take-up roll. 18 is a gas supply pipe, 19 is a power source for generating plasma, 20 and 21 are magnetic field generators, 30 is a vacuum chamber, 40 is a vacuum pump, 41 is a control unit, and S is It is a film formation space. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the other example of the film-forming apparatus which can be utilized suitably in order to manufacture the 1st gas barrier layer of the gas barrier film which concerns on this invention, and a 2nd gas barrier layer, 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, 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, and 19 and 19' are power sources for generating plasma. 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 (wherein 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) which satisfies the composition range and has a thickness of 50 to 1000 nm. Gas barrier layer; (E) SiO _y N _z (where 0.55 <y ≦ 2.0, 0.25 <z ≦ 0.66) and a thickness of 8 to 200 nm A gas barrier film comprising, in this order, a gas barrier film, and an electronic device body formed on a surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer; An electronic device. The electronic device of the present invention having such a configuration is excellent in durability in a high temperature and high humidity environment and excellent in impact resistance. In particular, when an organic EL element is used as the electronic device body, an electronic device in which the generation of dark spots is suppressed is obtained.

Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[(A) First gas barrier layer]
The (A) first gas barrier layer (hereinafter also simply referred to as layer (A)) according to the present invention contains an inorganic compound. Since the layer (A) is the layer that is exposed to the highest humidity conditions among the layers (A) to (E), the composition is hardly changed by humidity and stably exhibits gas barrier properties. It is preferable to form by the vapor phase film forming method.

The first gas barrier layer according to the present invention contains an inorganic compound. Although it does not specifically limit as an inorganic compound contained in a 1st gas barrier layer, For example, a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, or a metal oxycarbide is mentioned. Among these, oxides, nitrides, carbides, oxynitrides or oxycarbides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce and Ta in terms of gas barrier performance Are preferably used, and an oxide, nitride or oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti is more preferable, and in particular, a metal 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, or aluminum silicate. You may contain another element 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. More preferably, it is more 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 formation method of the first gas barrier layer is preferably a vapor deposition method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD).

Hereinafter, the vapor deposition method will be described.

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

Sputtering is a method in which a target is placed in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is collided with the target, and atoms on the target surface are ejected and adhered to the substrate. . At this time, a reactive sputtering method may be used in which an inorganic layer is formed by causing nitrogen and oxygen gas to flow into the chamber to react nitrogen and oxygen with an element ejected from the target by argon gas. .

The chemical vapor deposition method (Chemical Vapor Deposition, CVD method) is a method of depositing a film by supplying a source gas containing a target thin film component onto a substrate and performing a chemical reaction on the surface of the substrate or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The 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 film forming speed and processing area.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

In the following description, a case where the first gas barrier layer is manufactured by using a counter roll type roll-to-roll film forming apparatus that forms a thin film by a plasma CVD method will be described as an example of the film forming apparatus. 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 has a basic structure in which two film forming apparatuses 100 illustrated in FIG. 1 are joined in tandem. Here, the case where the gas barrier layer is formed will be described using the film forming apparatus illustrated in FIG. 2 as an example. However, the description regarding the film forming apparatus illustrated in FIG. 2 is the same as the description regarding the film forming apparatus illustrated in FIG. However, it is considered as appropriate.

As shown in FIG. 2, the film forming apparatus 101 includes a feed roll 10, transport rolls 11 to 14, first, second, third, and fourth film forming rolls 15, 16, 15 ′, 16 ′, Take-off roll 17, gas supply pipes 18, 18 ', plasma generation power sources 19, 19', magnetic field generators 20, 21, 20 ', 21', vacuum chamber 30, vacuum pumps 40, 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 take-up roll 17 are accommodated in the 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 it is below the glass transition temperature of the base material 1a, the thermal deformation of the base material can be suppressed.

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

When forming the first gas barrier layer using the film forming apparatus 101 (A), by transporting the substrate 1a in the forward direction and the reverse direction and reciprocating the film forming part S or the film forming part S ′, (A) The first gas barrier layer formation (film formation) step can be repeated a plurality of times.

The gas supply pipes 18 and 18 ′ supply a film forming gas such as a plasma CVD source gas 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. Furthermore, 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. In addition, the compounds described in paragraph “0075” of JP2008-056967 can also be used. Among the silicon compounds, it is preferable to use hexamethyldisiloxane (HMDSO) in the formation of the first gas barrier layer (A) from the viewpoint of easy handling of the compound and high gas barrier properties of the obtained gas barrier film. . Two or more silicon compounds may be used in combination. The source gas may contain monosilane in addition to the silicon compound.

As the film forming gas, a reactive gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to become a silicon compound such as oxide or 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, a discharge gas may be used as a film forming gas in order to generate plasma.

The pressure (degree of vacuum) in the vacuum chamber 30 can be adjusted as appropriate according to the type of source gas. The pressure of the film forming part 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 (the 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, there is little or no cracking in the gas barrier layer, and a gas barrier property suitable for the present invention can be obtained.

[(B) Buffer layer]
The (B) buffer layer (hereinafter also simply referred to as 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 configuration diffuses the moisture that has permeated through the layer (A) in the buffer layer to create a low humidity state. By diffusing moisture in this way, it is difficult to make the passage of moisture, and the role of moisture permeation can be suppressed.

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, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, fat Examples thereof include base materials containing a thermoplastic resin such as a ring-modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound. These resin substrates can be used alone or in combination of two or more.

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

The resin base material preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is preferably 0.01 nm or more for practical use. If necessary, the surface of the substrate may be polished to improve 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 above treatments may be combined as necessary. 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 an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

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

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

The pressure-sensitive adhesive contained in the adhesive layer is not particularly limited, and examples include acrylic pressure-sensitive adhesives, silicon pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. can do. Moreover, as an adhesive agent contained in an adhesive layer, an epoxy-type adhesive agent, a urethane type adhesive agent, etc. are mentioned, for example. In this adhesive layer, as additives, for example, stabilizers, surfactants, ultraviolet absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. Can also 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, each buffer layer may have the same composition or a different composition.

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. When the thickness is less than 10 μm, the diffusion of moisture that has passed through the first gas barrier layer becomes insufficient, and there is a possibility that moisture passage is formed and moisture permeation easily occurs. On the other hand, when it exceeds 200 μm, moisture permeates from the end (edge) of the buffer layer, and shrinkage 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 layer (C)) according to the present invention contains an inorganic compound as in the case of the (A) first gas barrier layer. Since the kind of inorganic compound contained in the second gas barrier layer and the content of the inorganic compound are the same as those in the first gas barrier layer (A), description thereof is omitted here.

The method for forming the second gas barrier layer is not particularly limited, but a vapor deposition method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD), 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 liquid containing polysilazane (hereinafter, also simply referred to as a coating film forming method) and the like can be mentioned. Among these, the vapor deposition method is preferable from the viewpoint that the composition hardly changes due to humidity and stably exhibits gas barrier properties.

Details of the vapor deposition method are the same as those described in the section of the first gas barrier layer (A) above, and thus the description thereof is omitted here. Below, the coating-film formation method is demonstrated.

<Coating method>
The second gas barrier layer according to the present invention is formed by applying energy to a coating film formed by applying a coating solution containing an inorganic compound, preferably a coating solution containing a silicon compound (coating method). (Film formation method). By applying this energy, the second gas barrier layer exhibits gas barrier properties. 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 solution containing a silicon compound can be prepared.

Among these, polysilazane such as perhydropolysilazane and organopolysilazane; polysiloxane such as silsesquioxane, etc. are preferable in terms of film formation, fewer defects such as cracks, and less residual organic matter, and high gas barrier performance. 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, such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer.

Specifically, the 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, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, 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 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 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 preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

Alternatively, 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, 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 to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that 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, aryl group, vinyl group or (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 the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ″, and q may be the same or different.

In addition, as the polysilazane, compounds described in paragraphs “0095” to “0097” of JP-A-2015-003464 and commercially available products can be used.

When polysilazane is used, the content of polysilazane in the second gas barrier layer before energy application may be 100% by mass when the total mass of the second gas barrier layer is 100% by mass. When the second gas barrier layer contains a material other than polysilazane, the content of polysilazane 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. More preferably, it is 70 mass% or more and 95 mass% or less.

(Second gas barrier layer forming coating solution)
Regarding the composition of the second gas barrier layer-forming coating solution, the coating method, the drying temperature of the coating film obtained after coating, the method for removing moisture from the coating film, etc., paragraphs “0092” to “0092” in JP-A-2015-033764. The conditions described in “0101” can be referred to as appropriate.

<Application of energy>
Subsequently, energy is applied to the coating film formed as described above to perform a conversion reaction of the silicon compound to silicon oxide or silicon oxynitride, and the second gas barrier layer exhibits gas barrier properties. The inorganic thin film is modified. As the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature and a conversion reaction by an ultraviolet irradiation treatment are preferable. As a specific method of this conversion reaction, the conditions described in paragraphs “0120” to “0123” and “0130” to “0145” of JP-A-2015-003464 can be appropriately referred to and employed. .

In the vacuum ultraviolet irradiation process, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane coating is preferably 1 mW / cm ² to 10 W / cm ² , more preferably 30 mW / cm ² to 200 mW / cm ^{2. preferably,} further preferably at 50mW / cm 2 ~ 160mW / cm 2. If it is the said range, the modification | reformation efficiency will become enough and the ablation of a coating film and the damage to a base material can be suppressed.

The amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the coating 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 . If it is the said range, modification | reformation will become enough and a crack generation and the thermal deformation of a base material can be suppressed.

Further, the vacuum ultraviolet ray to be used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods 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 consist of only a layer formed by a vapor deposition method or may be formed by a coating film formation 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, the second gas barrier layer is preferably formed by a vapor deposition method from the viewpoint that the composition hardly changes with humidity and high gas barrier properties 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. If it is this range, the balance of gas-barrier property and impact resistance will become favorable, and it 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 (where 0.20 <w ≦ 0.55, 0.66 ≦ x <0.75) and has a thickness of 50 nm to 1000 nm. It is a layer.

The layer (D) has a gas barrier property, but also functions as a so-called desiccant layer that traps water vapor by reacting with water vapor that has gradually entered. For example, by setting the order of layer (A) / layer (B) / layer (C) / layer (D), most of the water vapor entering from the layer (A) side reaches the layer (C). Is barriered. However, in some cases, water vapor may enter slightly from the defective portion of the layer (C). A higher gas barrier property can be exhibited by capturing the water vapor by the layer (D).

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, since the total amount of the compound that reacts with water vapor as a desiccant is reduced, the amount of water vapor that can be captured is limited, and the desiccant function is lost within the service life required for the device. There is a possibility that the barrier property is lowered. On the other hand, when the thickness exceeds 1000 nm, for example, when the layer (D) is formed by modification by application of energy, the modification may be insufficient and the barrier property may be lowered, and the cost may be increased. Moreover, in the layer containing the layer (D), the occurrence of cracks is concerned, and the productivity is also lowered.

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 costs are further improved during the service life required for the device.

As long as the layer (D) exists between the layer (C) and the (E) fourth gas barrier layer described later, the layer (D) may be present as one continuous layer, or two or more It may be a form that exists 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 in the above range.

A person skilled in the art can adjust the Si / O / N composition ratio and thickness in 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 (C) the second gas barrier layer. In this case, the coating liquid containing the silicon compound Thickness, degree of drying after application, amount of energy to be applied (for example, when applying energy by irradiating vacuum ultraviolet light, 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, if the amount of energy applied is reduced, oxygen can be reduced in the composition ratio of the layer (D). Further, when the thickness of the coating solution containing a silicon compound is increased, the thickness of the layer is increased. Therefore, those skilled in the art can adjust the thickness of the coating film in accordance with the target layer thickness.

The layer (D) can also be formed by a vapor deposition method, but when the vapor deposition method is employed, there is a concern that the cost may increase due to the complexity of the deposition process. From the viewpoint of cost reduction, a coating film forming method is preferable, and a method of applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane is more preferable.

For the details of the type of solvent and polysilazane used in the coating solution (third gas barrier layer forming coating solution) used in the coating film forming method, the coating method and the drying method, and the energy application method described above (C ) Since it is the same as that described in the section of the second gas barrier layer, detailed description is omitted here. Application of energy is preferably performed by vacuum ultraviolet rays from the viewpoint of reforming efficiency (effect of improving gas barrier properties with respect to applied energy).

When the layer (D) is formed by the coating film forming method, the coating liquid (coating film) after drying is preferably applied to a thickness such that the thickness is 60 nm to 1000 nm, more preferably 100 nm to 300 nm. What is necessary is just to apply | coat a liquid. Further, the amount of energy to be applied is preferably 500 mJ / cm ² to 10 J / cm ² , more preferably 1 J / cm ² to 8 J / cm ² . Furthermore, the oxygen concentration in the atmosphere when energy is applied is preferably 0.001 to 2% by volume, more preferably 0.005 to 1% by volume.

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

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

The XPS analysis in the present invention is performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

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

<< XPS analysis conditions >>
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time is adjusted so that the thickness is about 2.8 nm in terms of SiO _2.・ Quantification: The background is obtained by the Shirley method, and the relative sensitivity coefficient method is calculated from the obtained peak area. And quantified. Data processing uses MultiPak manufactured by ULVAC-PHI.

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

Also, a cross section of each sample is photographed with a TEM, and each film thickness of the laminated structure is obtained. The composition distribution profile 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 for obtaining the thickness per layer from a TEM image, a gas barrier film is prepared by using the following FIB processing apparatus, and then a cross-section TEM observation is performed according to a conventional 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》
・ Apparatus: SII SMI2050
・ Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
<< TEM observation >>
Apparatus: JEM2000FX (acceleration 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 layer (E)). The layer (E) satisfies the composition range represented by SiO _y N _z (where 0.55 <y ≦ 2.0, 0.25 <z ≦ 0.66) and has a thickness of 8 nm to 200 nm. It is a layer.

Layer (E) has a very high gas barrier property. The layer (E) is less reactive with water vapor than the layer (D) and has a small composition change even under high temperature and high humidity, so that it can maintain a very high gas barrier property over a long period of time. In the order of layer (A) / layer (B) / layer (C) / layer (D) / layer (E), water vapor that could not be trapped in layer (D) was almost completely blocked in layer (E). The Thereby, the invasion of water vapor into the electronic device main body provided immediately above the layer (E) can be prevented, and for example, the occurrence of dark spots in the organic EL element can be suppressed.

The thickness of the layer (E) is 8 nm or more and 200 nm or less. When the thickness of the layer (E) is less than 8 nm, there is a possibility that the water vapor is not sufficiently blocked. On the other hand, if it exceeds 200 nm, the improvement in gas barrier properties accompanying the increase in film thickness is saturated, and the productivity is also lowered, so that no cost merit is 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 during the service life required for the device, for example, the generation of dark spots when used in organic EL elements is suppressed, and even if dark spots are generated, the growth can be achieved. The effect which can be suppressed further improves.

As long as the layer (E) is present between the layer (D) and the electronic device body, the layer (E) may be present as one continuous layer, or as two or more layers. Form may be sufficient. When two or more layers (E) exist, the sum (total thickness) of the thicknesses of all the layers (E) may be in the above range.

A person skilled in the art can adjust the Si / O / N composition ratio and thickness in 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 of (C) the second gas barrier layer. In this case, the coating liquid containing the silicon compound 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, if the amount of energy to be applied is increased, oxygen can be increased in the composition ratio of the layer (E). Further, when the thickness of the coating solution containing a silicon compound is increased, the thickness of the layer is increased. Therefore, those skilled in the art can adjust the thickness of the coating film in accordance with the target layer thickness.

The layer (E) can also be formed by a vapor deposition method. However, when the vapor deposition method is employed, there is a concern that the cost may increase due to the complexity of the deposition process. From the viewpoint of cost reduction, a coating film forming method is preferable, and a method of applying energy to a coating film obtained by applying and drying a coating liquid containing polysilazane is more preferable.

For the details of the type of solvent and the type of polysilazane used in the coating solution (fourth gas barrier layer-forming coating solution) used in the coating film forming method, the coating method and the drying method, and the energy application method described above (C ) Since it is the same as that described in the section of the second gas barrier layer, detailed description is omitted here. Application of energy is preferably performed by vacuum ultraviolet rays from the viewpoint of reforming efficiency (effect of improving gas barrier properties with respect to applied energy).

When the layer (E) is formed by the coating film forming method, the coating liquid (coating film) after drying is preferably applied with a thickness of 10 nm to 200 nm, more preferably 20 nm to 150 nm. What is necessary is just to apply | coat a liquid. The amount of energy to be applied is preferably 500 mJ / cm ² to 10 J / cm ² , more preferably 1 J / cm ² to 8 J / 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 in the thickness direction of such a layer (E) can be obtained by measurement by a method using XPS (photoelectron spectroscopy) analysis as described above.

[Layers with various functions]
In the gas barrier film according to the present invention, layers having various functions can be provided.

(Anchor coat layer)
An anchor coat layer is formed on the surface of the buffer layer on the side on which 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. Also good.

As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned 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, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

Also, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an 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 on which protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. Provided for. Such a smooth layer is basically produced 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 a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

Specific examples of thermosetting materials include Tutprom Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (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 Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. 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 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 an evaporation 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-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation 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 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 10-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a barrier layer is apply | coated with an application | coating form, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability is impaired. 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 opposite to the surface having the buffer layer of the first gas barrier layer. By having the protective layer, the electronic device of the present invention is a device with higher durability (long-term reliability). 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 unitary unsaturated organic compound having one polymerizable unsaturated group in the molecule An agent can be mentioned.

) Matting agents may be added as other additives. 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. .

The protective 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 protective layer as described above is prepared as a coating liquid with a hard coating agent, a matting agent, and other components as necessary, and appropriately prepared as a coating solution using a diluent solvent, and the coating solution is used as a support film. After coating on the surface by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing.

As a method of irradiating with ionizing radiation, ultraviolet rays having 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 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 protective layer is preferably in the range of 50 to 5000 nm, and more preferably in the range of 100 to 2000 nm.

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

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

[Electronic device manufacturing method]
The electronic device of the present invention is not particularly limited, but is preferably obtained by the following production 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 a surface of the resin base material opposite to the surface on which the first gas barrier layer is formed Forming a second gas barrier layer, a third gas barrier layer, and a fourth gas barrier layer in order from the resin substrate side to obtain a gas barrier film; and forming an electronic device body on the fourth gas barrier layer And a manufacturing method comprising:

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

(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. Using the adhesive or pressure-sensitive adhesive, the step of forming the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer in order from the substrate side to obtain a second barrier film, 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. The manufacturing method including the process of bonding the surface on the opposite side of the done side, and the process of forming the said electronic device main body on a said 4th gas barrier layer.

(5) 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 the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer in order from the substrate side to obtain a second barrier film; and the second barrier film of the second barrier film. 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 an adhesive, and the second barrier. Bonding the second gas barrier layer, the third gas barrier layer, the fourth gas barrier layer, and the surface opposite to the side on which the electronic device main body is formed of the conductive film. Method.

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

In the electronic device obtained by the manufacturing method of (4) or (5), the first resin base material is provided on the outer side (side closer to the outside air) than the first gas barrier layer. Such an embodiment is also a category of the electronic device of the present invention.

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

[Absorptance of light having a 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%. The use of the gas barrier film according to the present invention having a low light absorptivity (that is, high transmittance) at a wavelength of 450 nm for a display device enables the wavelength of 450 nm related to blue light in the process of visible light reaching from the light source to the user. Absorption of the nearby light by the gas barrier film can be suppressed as much as possible.

By having the layer (D) and the layer (E), the absorption rate 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 absorptivity at 450 nm is preferably less than 15%, more preferably less than 10%, and further preferably less than 8%. The lower limit of the absorptance at 450 nm is not particularly limited, but is substantially 0% or more, for example.

The absorptance at 450 nm can be measured with a spectrophotometer or a spectrocolorimeter. The absorptance at 450 nm is obtained by, for example, measuring a transmittance A (%) and a reflectance B (%) at 450 nm using a spectrocolorimeter (for example, CM-3600d, manufactured by Konica Minolta Co., Ltd.). What is necessary is just to obtain | require using.

In the gas barrier film according to the present invention, the transmittance in the visible light region (400 to 700 nm) is preferably 80% or more, and 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 characteristics over 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 is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air.

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 effects 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 effect 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 only to the following examples.

[Resin substrate]
Base material: 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: 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 in which two apparatuses each having a film forming unit composed of opposing film forming rolls described in Japanese Patent No. 4268195 are connected (having a first film forming unit and a second film forming unit) A film forming apparatus was used (see FIG. 2). The effective film formation width is 1000 mm, and the film formation conditions are: conveyance speed, supply amount of source gas (HMDSO) of each of the first film formation unit and the second film formation unit, supply amount of oxygen gas, degree of vacuum, applied power, The frequency was adjusted by the frequency of the power supply and the number of film formation (number of passes of the apparatus). In contrast to the first pass, the substrate is transported in the direction of rewinding the substrate in the second pass. However, even when the pass directions are different, the first film forming unit passes through the first film forming unit, and the component that passes next. The film part was used as the second film forming part.

As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 30 ° C. As the substrate used, a substrate obtained by pasting and winding a heat-resistant protective film on the surface opposite to the film formation surface was used. In the case of film formation on both sides, a heat-resistant protective film is further bonded to the film-formed surface of the base material after single-sided film formation, and then the protective film on the opposite surface, which is the next film formation surface, is peeled off. What was wound up was used. The film thickness was determined by cross-sectional TEM observation.

The film forming conditions of the first film forming unit and the second film forming unit 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 liquid 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 (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a dibutyl ether solution (NAX120-20, manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of perhydropolysilazane in 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.

A base material on which a gas barrier layer was formed or the above base material was cut out into a sheet shape and prepared. Layer formation by coating was performed on the already formed gas barrier layer surface or on the smooth surface of the substrate. The coating solution was applied by spin coating so as to have a dry film thickness shown in Table 2 below, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to a vacuum ultraviolet ray irradiation treatment using an Xe excimer lamp having a wavelength of 172 nm 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 A gas barrier layer was formed.

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

The composition distribution in the thickness direction of the third gas barrier layer and the fourth gas barrier layer was determined by measurement using the following XPS analysis method.

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

Thus, primary data of the profile of the composition distribution in the film thickness direction in the third gas barrier layer and the fourth gas barrier layer were obtained. The obtained composition distribution profile in the film thickness direction is corrected 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. The thickness was determined.

For the first gas barrier layer, the buffer layer, and the second gas barrier layer, the cross section was photographed with 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 35 μm-thick thin film glass onto a 50 μm-thick PET film (product name: Lumirror (registered trademark) 50U48, manufactured by Toray Industries, Inc.).

(Comparative Example 4)
A second gas barrier layer was formed on one surface of the base material under the condition of V3. Next, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P3 and P1, and a third gas barrier layer and a fourth gas barrier layer were provided to produce a gas barrier film.

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

(Example 2)
A first gas barrier layer was formed on one surface of the base material under the condition V2. Next, a second gas barrier layer was formed on the surface of the base material opposite to the side on which the first gas barrier layer was formed under the condition of V3. Next, a gas barrier layer was formed on the second gas barrier layer under the conditions of 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 conditions of V1. Next, a second gas barrier layer was formed on the surface of the base material opposite to the side on which the first gas barrier layer was formed under the condition of V3. Next, a gas barrier layer is sequentially formed on the second gas barrier layer under the condition of P3, the condition of P3, and the condition of P1, and a third gas barrier layer and a fourth gas barrier layer are provided to provide gas barrier properties. A film was prepared.

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

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 hardened | cured by the irradiation energy amount 2J / cm < ² > using the high pressure mercury lamp in the air, and it was set as the hard-coat layer.

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

(Example 5)
A barrier film 1 in which a first gas barrier layer was formed on one surface of the substrate A under the conditions of V1 was prepared. 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 1 on which the gas barrier layer is not formed is a transparent adhesive (manufactured by Sekisui Chemical Co., Ltd., High-transparent double-sided tape 5402, 25 μm thick) was used to produce a gas barrier film.

(Example 6)
A second gas barrier layer was formed on one surface of the base material under the conditions of P3. Next, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P3 and P1 to prepare a barrier film 2 provided with a third gas barrier layer and a fourth gas barrier layer. Separately, a barrier film 1 in which a first gas barrier layer was formed on one surface of the base material under the conditions of V1 was prepared. A transparent adhesive (manufactured by Sekisui Chemical Co., Ltd., highly transparent double-sided tape 5402, 25 μm thickness) is used for the first gas barrier layer of the barrier film 1 and the surface of the barrier film 2 where the gas barrier layer is not formed. And bonded to produce a gas barrier film.

(Comparative Example 6)
A barrier film 1 in which a first gas barrier layer was formed on one surface of the substrate A under the conditions of 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 in Comparative Example 4 on which the gas barrier layer is not formed are formed with a transparent adhesive (Sekisui A gas barrier film was prepared by bonding using a highly transparent double-sided tape 5402, 25 μm thickness, manufactured by Chemical Industry Co., Ltd.

(Example 7)
A barrier film 1 was prepared in which a first gas barrier layer was formed on one surface of the substrate A by sputtering 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 is not formed is transparent adhesive (Sekisui Chemical Co., Ltd., highly transparent A double-sided tape 5402, 25 μm thick) was used to produce a gas barrier film.

(Comparative Example 7)
A second gas barrier layer was formed on one surface of the base material under the condition of V3. Next, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P2 and P1, and a third gas barrier layer and a fourth gas barrier layer were provided to produce a barrier film 2. .

A gas barrier film was produced in the same manner as in Example 5 except that the above-described 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 base material under the condition of V3. Next, a gas barrier layer was formed on the second gas barrier layer under the conditions of 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-described 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 base material under the above-mentioned conditions of V3 to produce a gas barrier film.

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

The protective 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 500 nm, and then dried at 80 ° C. for 3 minutes. Then, it hardened | cured by the irradiation energy amount of 0.5 J / cm < ² > using the high pressure mercury lamp in the air, and it was set as the protective layer.

(Comparative Example 10)
On the first gas barrier layer of the gas barrier film obtained in Example 3, an organic EL element described later was formed.

(Comparative Example 11)
A gas barrier film having a gas barrier layer formed on one surface of the base material under the above-mentioned conditions of V1 was prepared. The surface of the film on which the gas barrier layer is not 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 combined with a transparent adhesive (manufactured by Sekisui Chemical Co., Ltd. A transparent double-sided tape 5402, 25 μm thick) was used to produce a gas barrier film.

Example 9
A second gas barrier layer was formed on one surface of the base material under the conditions of P3. Subsequently, a gas barrier layer was sequentially formed on the second gas barrier layer under the conditions of P3 and P1 to produce a barrier film 2 provided with a third gas barrier layer and a fourth gas barrier layer. . Further, an organic EL element to be described later was formed on the fourth gas barrier layer of the barrier film 2.

Separately, a barrier film 1 in which a first gas barrier layer was formed on one surface of the base material under the conditions of V1 was prepared. A transparent pressure-sensitive adhesive (manufactured by Sekisui Chemical Co., Ltd., highly transparent double-sided tape 5402, 25 μm thickness) is applied to the first gas barrier layer of the barrier film 1 and the surface of the barrier film 2 where the organic EL element is not formed. The electronic device was produced by using and bonding.

(Example 10)
On the fourth gas barrier layer of the gas barrier film obtained by the same method as in Comparative Example 4, an organic EL element described later was formed. 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 above-mentioned conditions of V4 to produce an electronic device.

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

≪Method for manufacturing organic EL element≫
Using the glass plates prepared in Comparative Examples 1 and 2, the composite film prepared in Comparative Example 3, and the gas barrier films obtained in Examples 1 to 8 and Comparative Examples 4 to 11, the following method was used. 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. In addition, although the preparation method of the organic EL element at the time of using a gas-barrier film is shown below, the organic EL element was produced with the same method also in the glass plate and the composite film.

(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after reducing the pressure in the first vacuum tank of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.

Next, the base material formed up to the base layer was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

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

Next, compound A-3 (blue light-emitting dopant), compound A-1 (green light-emitting dopant), compound A-2 (red light-emitting dopant) and compound H-1 (host compound) are formed. In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35% to 5% by mass, and the compound A-1 and the compound A-2 each had a concentration of 0.2% by mass without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / second, the vapor deposition rate was changed depending on the location so that the compound H-1 was 64.6% by mass to 94.6% by mass, so that the thickness was 70 nm. A light emitting layer was formed.

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

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

(Solid sealing)
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. 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.

Next, the sample was placed in a decompression device, and pressed at 90 ° C. under a reduced pressure of 0.1 MPa, pressed against the superposed base material and the sealing member, and held for 5 minutes. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with 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 performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

In this way, four electronic devices having a light emitting region size of 5 cm × 5 cm were prepared for one level.

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

Note that 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 device obtained as described above was energized for 300 hours in an environment of 85 ° C. and 85% RH, and for the generated dark spots, the number of generated dark spots having a circle-equivalent diameter of 200 μm or more was determined. The average was obtained for four devices.

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

The above evaluation results are shown in Table 4 below.

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

Note that this application is based on Japanese Patent Application No. 2014-56840 filed on March 19, 2014, the disclosure of which is incorporated by reference in its entirety.

Claims (7)

(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) No. 1 which satisfies the composition range represented by SiO _w N _x (where 0.2 <w ≦ 0.55, 0.66 <x ≦ 0.75) and has a thickness of 50 to 1000 nm. 3 gas barrier layers;
(E) SiO _y N _z (where 0.55 <y ≦ 2.0, 0.25 <z ≦ 0.66) and satisfying the composition range and having a thickness of 8 to 200 nm. 4 gas barrier layers;
A gas barrier film containing
An electronic device body formed on a surface of the fourth gas barrier layer opposite to the surface having the third gas barrier layer;
Including electronic devices. 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 apply and dry a coating liquid containing polysilazane. The electronic device according to claim 1, wherein the electronic device is formed by applying energy to a coating film obtained in this way. The electronic device according to claim 2, wherein the application of the energy is performed by irradiating with vacuum ultraviolet rays. The electronic device according to any one of claims 1 to 3, wherein the gas barrier film has an absorptance of light having a wavelength of 450 nm of less than 15%. The electronic device according to any one of claims 1 to 4, further comprising a protective layer on a surface of the first gas barrier layer opposite to the surface having the buffer layer. The electronic device is
Forming a second gas barrier layer, a third gas barrier layer, and a fourth gas barrier layer in order from the resin substrate side on one surface of the resin substrate to be the buffer layer;
Forming an electronic device body on the fourth gas barrier layer;
A first gas barrier layer is formed on a surface opposite to the surface on which the second gas barrier layer, the third gas barrier layer, the fourth gas barrier layer, and the electronic device main body are formed of the resin base material. And a process of
The electronic device according to claim 1, wherein the electronic device is manufactured by a manufacturing method including: The electronic device is
Forming the first gas barrier layer on one surface of the first resin base material to obtain a first barrier film;
A second barrier property is formed by forming the second gas barrier layer, the third gas barrier layer, and the fourth gas barrier layer in this order on the one surface of the second resin substrate from the second resin substrate side. 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, and the second gas barrier layer and the third gas barrier layer of the second barrier film. Bonding the fourth gas barrier layer and the surface opposite to the side on which the electronic device body is formed;
The electronic device according to any one of claims 1 to 5, which is obtained by a production method comprising:

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