WO2015190572A1

WO2015190572A1 - Gas barrier film laminate and electronic component employing same

Info

Publication number: WO2015190572A1
Application number: PCT/JP2015/066934
Authority: WO
Inventors: 國信　隆史; 正志橋本; 慧七里
Original assignee: Jnc株式会社
Priority date: 2014-06-13
Filing date: 2015-06-11
Publication date: 2015-12-17
Also published as: JPWO2015190572A1; TW201601914A

Abstract

　The purpose of the present invention is to obtain a gas barrier film laminate provided with a gas barrier film having satisfactory gas barrier properties, with which the cohesion of the gas barrier layer can be improved during formation of the gas barrier layer by a plasma CVD process. This gas barrier film laminate is provided with: a resin film (11) serving as a base material; a cohesive layer (13) formed on at least one surface side of the resin film (11), the cohesive layer (13) containing a compound the composition of which includes SiO_x and which satisfies the expression 1.8 < x < 2.2, or a cohesive layer (13) containing a compound the composition of which includes SiCy and which satisfies the expression 0 < y < 0.15; and a gas barrier layer (14) formed over the cohesive layer (13), the gas barrier layer (14) containing a compound the composition of which includes SiO_xC_y, and which satisfies the expressions 1.1 ≦ x ≦ 1.9 and 0 ≦ y ≦ 1.9.

Description

Gas barrier film laminate and electronic component using the same

The present invention relates to a gas barrier film laminate. In particular, the present invention relates to a gas barrier film laminate in which water vapor permeation to electronic components can be effectively suppressed, and further, layer peeling is suppressed.

Conventionally, in an organic electroluminescence element (hereinafter also referred to as an OLED element), an organic solar cell element (hereinafter also referred to as an OPV element), a liquid crystal element, etc., an inorganic filler is formed on a glass or plastic film having a high barrier property. A gas barrier film laminate in which a mixed / dispersed resin composition film or metal oxide thin film is formed has been used.
However, in a gas barrier film laminate composed of multiple layers, there is a problem of adhesion between a plastic film and a resin composition film or a metal oxide thin film.
Cited Document 1 discloses “an article including a base material and a barrier layer which is provided on the surface of the base material and has a moisture and oxygen permeation resistance” (paragraph 0007). Further, as an additional layer, It is disclosed to provide an adhesive layer (paragraph 0025, FIG. 1) that enhances the adhesion of the barrier layer to the substrate.

As a method for forming a thin film of a metal oxide or the like as a gas barrier layer on the surface of a plastic film, a chemical vapor deposition method, for example, a plasma chemical vapor deposition method (CVD) is known. However, the plasma CVD method has a problem of abrupt compressive stress generated during film formation and curling due to this, and a thin film such as a metal oxide as a gas barrier layer needs to improve its adhesion. .

JP 2004-160977 A

The present invention has been made in view of the above-described problems of the prior art, and improves the adhesion of the gas barrier layer in the formation of a gas barrier layer by a plasma CVD method using an organometallic compound as a raw material, and a sufficient gas barrier. It is an object of the present invention to provide a gas barrier film laminate having properties.

As a result of intensive research to solve the above problems, the present inventors have been able to form an adhesion layer by changing the composition of the film forming gas during film formation by the plasma CVD method. It has been found that the adhesion of the layer can be improved (hardly peeled off), and the present invention has been completed.

The gas barrier film laminate according to the first aspect of the present invention includes, for example, as shown in FIG. 1 (a), a resin film 11 as a base material; and a film formed on at least one side of the resin film 11. Adhesion layer 13 containing a compound containing SiO _x in the composition satisfying 8 <x <2.2, or Adhesion layer 13 containing a compound containing SiC _y in the composition satisfying 0 <y <0.15 ; was deposited on the adhesion layer 13, meet the 1.1 ≦ x ≦ 1.9,0 ≦ y ≦ 0.9, and a gas barrier layer 14 comprising a compound containing _SiO x _{C y} in the composition . Note that “single-sided” refers to stacking on one side with or without contact. “Up” refers to laminating in contact. The “compound containing ˜ in the composition” may be a compound containing ˜ in the composition.
If comprised in this way, a gas barrier layer can be firmly adhere | attached on another layer by mediating an adhesion layer.

In the gas barrier film laminate according to the second aspect of the present invention, in the gas barrier film laminate according to the first aspect of the present invention, the thickness of the adhesion layer 13 is 10 to 500 nm.
If comprised in this way, a contact | adherence layer will express sufficient adhesiveness, and upper and lower 2 layer which pinches | interposes a contact | adherence layer can be adhered more firmly.

The gas barrier film laminate according to the third aspect of the present invention is the gas barrier film laminate according to the first aspect or the second aspect of the present invention, wherein the adhesion layer 13 and the gas barrier layer 14 are continuously formed by a plasma CVD method. The ratio of the reactive gas in the film forming gas when forming the adhesion layer 13 is larger than the ratio of the reactive gas in the film forming gas when forming the gas barrier layer 14. The “film formation gas” refers to a gas used during film formation, such as a source gas, a reactive gas, a carrier gas, and a discharge gas. The “source gas” is a gas that can form a thin film with a single source gas or a thin film with a combination of a source gas and an auxiliary gas. The “reactive gas” is an auxiliary gas that cannot form a thin film such as a gas barrier layer or an adhesion layer by itself, for example, a gas for oxidizing or nitriding a raw material compound.
If comprised in this way, the elemental composition of the interface vicinity of an adhesion layer and a gas barrier layer can be changed by changing the film-forming conditions of a plasma CVD method, and the adhesiveness of a gas barrier layer can be improved. Moreover, only the ratio of the reactive gas is changed, and the adhesion layer and the gas barrier layer can be formed efficiently, so that the productivity can be improved and the production cost can be reduced. Furthermore, since the adhesion layer and the gas barrier layer are formed by a plasma CVD method, a dense and flexible film can be formed. Therefore, defects and peeling are less likely to occur compared to other methods, and the gas barrier layer can have high gas barrier properties.

The gas barrier film laminate according to the fourth aspect of the present invention is the gas barrier film laminate according to the third aspect of the present invention, wherein the ratio of the reactive gas in the deposition gas during the formation of the adhesion layer 13 is The ratio of the reactive gas in the film-forming gas when forming the gas barrier layer 14 is 1.2 to 4.0 times.
If comprised in this way, the contact | adherence layer with an appropriate elemental composition can be formed.

The gas barrier film laminate according to the fifth aspect of the present invention is the gas barrier film laminate according to any one of the first to fourth aspects of the present invention, wherein the resin film 11 is polyethylene terephthalate, It is a film mainly composed of a resin which is polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof. The “main component” means containing 50% by weight or more of the compound.
If constituted in this way, these resin films are preferred because of their excellent cost and availability. Moreover, resin according to a use, such as making it transparent, can be selected suitably.

The gas barrier film laminate according to the sixth aspect of the present invention is the gas barrier film laminate according to any one of the first to fifth aspects of the present invention, wherein water vapor at 40 ° C. and 90% RH is used. The transmittance is 0.005 g / m ² / day or less.
If comprised in this way, a gas barrier film laminated body can be used for electronic elements, such as an OLED element and OPV element by which high gas barrier property is calculated | required.

The gas barrier film laminate according to the seventh aspect of the present invention is the gas barrier film laminate according to any one of the first to sixth aspects of the present invention, for example, as shown in FIG. Thus, the organic film layer 12 sandwiched between the resin film 11 and the adhesion layer 13 is provided.
If comprised in this way, the unevenness | corrugation of the surface of a lower layer (resin film) from an organic film layer can be planarized by providing an organic film layer. Further, the organic film layer can suppress the curling of the gas barrier film laminate due to the residual stress generated in the formation process of the adhesion layer and the gas barrier layer.

The gas barrier film laminate according to the eighth aspect of the present invention is obtained by photopolymerizing the photocurable resin composition in the gas barrier film laminate according to the seventh aspect of the present invention. Layer.
If comprised in this way, since the photocurable resin composition is used, manufacture of an organic film layer becomes easy and production efficiency can be raised.

The electronic component according to the ninth aspect of the present invention includes, for example, an electronic element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes, as shown in FIG. The gas barrier film laminate 10 according to any one of the first to eighth aspects of the present invention to be protected is provided. “Protecting from water vapor” is typically performed by enclosing the electronic device, in addition to enclosing the entire electronic device, as well as enclosing the entire device together with other protective bodies. Is also included.
When configured in this way, the gas barrier film laminate is excellent in gas barrier properties, so that it is possible to prevent water vapor and oxygen from penetrating into the inside of the electronic element to deteriorate components constituting the electronic element and suppress performance from being deteriorated. it can.

The electronic component according to a tenth aspect of the present invention is the electronic component according to the ninth aspect of the present invention, wherein the gas barrier film laminate is transparent, and the electronic element is an OLED element or an OPV element. “Transparent” means a state in which the gas barrier film laminate transmits visible light and the opposite side of the gas barrier film laminate can be seen through.
If comprised in this way, when it uses for an OLED element, since the light emission from an element is not prevented, luminous efficiency is not deteriorated. Moreover, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side.

According to the present invention, it is possible to improve the adhesion of a gas barrier layer formed by a plasma CVD method and provide a gas barrier film laminate having a sufficient gas barrier property. Furthermore, the gas barrier film laminate can be used to protect electronic elements such as OLED elements and OPV elements from intrusion of water vapor.

(A) of FIG. 1 is the schematic of the gas barrier film laminated body 10 which concerns on the 1st Embodiment of this invention. FIG. 1B is a schematic view of a gas barrier film laminate 10 ′ according to the second embodiment of the present invention. (A) of FIG. 2 is the schematic of the electronic component which has an OLED element by a solid sealing system. FIG. 2B is a schematic view of an electronic component using the gas barrier film laminate 10 of the present invention as an alternative. FIG. 3 is a schematic view of another electronic component using the gas barrier film laminate 10 of the present invention. FIG. 4A is a schematic view of an electronic component having an OLED element with a conventional hollow structure. FIG. 4B is a schematic view of an electronic component using the gas barrier film laminate 10 of the present invention as an alternative. FIG. 5 is a schematic view of a roll-to-roll system. FIG. 6 is an XPS depth profile of the first embodiment. FIG. 7 is an XPS depth profile of the second embodiment. FIG. 8 is an XPS depth profile of Comparative Example 1. FIG. 9 is an XPS depth profile of Comparative Example 2.

This application is based on Japanese Patent Application No. 2014-122794 filed on June 13, 2014 in Japan, the contents of which form part of the present application. The present invention will be more fully understood from the following detailed description. Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, the detailed description and specific examples are preferred embodiments of the present invention and are described for illustrative purposes only. From this detailed description, various changes and modifications will be apparent to those skilled in the art within the spirit and scope of the invention. The applicant does not intend to contribute any of the described embodiments to the public, and modifications and alternatives that may not be included in the scope of the claims within the scope of the claims are also subject to equivalence. As part of the invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same or similar reference numerals, and redundant description is omitted. Further, the present invention is not limited to the following embodiments.

[Gas barrier film laminate 10]
The gas barrier film laminate 10 according to the first exemplary embodiment of the present invention includes, as shown in FIG. 1A, for example, a resin film 11 serving as a base material and an adhesion formed on at least one side of the resin film. A layer 13 and a gas barrier layer 14 formed on the adhesion layer 13 are provided.
The adhesion layer 13 and the gas barrier layer 14 are preferably continuously formed by a plasma CVD method. By changing the film formation conditions of the plasma CVD method, the composition of elements in the vicinity of the interface between the adhesion layer 13 and the gas barrier layer 14 can be changed, and the adhesion of the gas barrier layer can be improved (hard to peel off).

[Resin film 11]
The resin film 11 serving as the base material of the gas barrier film laminate 10 is not particularly limited as long as it is formed of an organic material that can hold each layer laminated on the resin film 11.

For example, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), cycloolefin polymer, aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, acrylic ester polymer, methacrylic ester polymer, polyimide, polyetherimide, etc. Heat-resistant transparent film based on sesquioxane (product name: Sila-DEC, manufactured by JNC Co., Ltd.), resin film made by laminating two or more layers of the above plastic, The composite film of resin-impregnated glass cloth and the like. From the viewpoint of cost and availability, a film mainly composed of polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof can be preferably used.

The thickness of the resin film is not particularly limited, but is preferably 20 to 500 μm, more preferably 30 to 300 μm. When the thickness is 20 μm or more, the rigidity as a base material is not sufficient, and stability does not decrease during film formation on a roll-to-roll basis. Further, when the thickness is 500 μm or less, it is possible to avoid that the flexibility is lowered and the cost is increased.

Furthermore, if the resin film is transparent, the gas barrier layer and the like laminated on the resin film are also transparent, so that a transparent gas barrier film laminate can be obtained. A transparent gas barrier film laminate can be used as a substrate such as an OLED element or an OPV element.

[Adhesion layer 13 / gas barrier layer 14]
It is preferable from the viewpoint of productivity that the adhesion layer 13 and the gas barrier layer 14 included in the gas barrier film laminate 10 illustrated in FIG. 1A are continuously formed by a plasma CVD method.
As shown in FIG. 6, the adhesion layer 13 and the gas barrier layer 14 are films in which the composition ratio of the compound to be contained is changed. For example, the adhesion layer 13 and the gas barrier layer 14 may be films containing an organic component whose main component is a metal oxide. Further, it may be a single film or a composite film. Note that a film mainly containing a metal nitride or a mixture of a metal oxide and a metal nitride may be used instead of the metal oxide.
Alternatively, the adhesion layer 13 contains a compound containing SiO _x in the composition satisfying 1.8 <x <2.2, or containing a compound containing SiCy in the composition satisfying 0 <y <0.15. To do. As the compound containing SiO _x on the composition, to form a composition of SiO _x repeatedly bound elemental Si and O, Similarly _SiO x _C _y, SiO _x N _y, a composition such as SiO _x N y _{C z} Examples of the material to be formed (0 ≦ y, 0 ≦ z), a group of molecules such as SiO ₂ , or a mixture thereof. The same applies to SiCy. The adhesion layer 13 preferably contains, as a main component, a compound containing SiO _x in the composition or a compound containing SiC _y in the composition.
The gas barrier layer 14 contains a compound containing SiO _x C _{y in the} composition that satisfies 1.1 ≦ x ≦ 1.9 and 0 ≦ y ≦ 0.9. The gas barrier layer 14 preferably contains a compound containing SiO _x C _y as a main component.

The thickness of the adhesion layer is preferably 10 to 500 nm, more preferably 30 to 400 nm, and still more preferably 50 to 250 nm in terms of the SiO ₂ equivalent film thickness. When it is 10 nm or more, sufficient adhesion is expressed. When the thickness is 500 nm or less, the gas barrier film laminate can be prevented from becoming too thick.
The thickness of the gas barrier layer is preferably 0.2 to 2 μm in terms of SiO ₂ thickness, more preferably 0.3 to 1.5 μm, and even more preferably 0.4 to 1.0 μm, resulting in good film thickness uniformity. Excellent gas barrier performance. When the thickness is 2 μm or less, generation of cracks due to bending can be suppressed.

As a method of forming a metal oxide thin film on the surface of a plastic substrate or the like, a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method, an ion plating method, a thermochemical vapor deposition method, There is chemical vapor deposition (CVD) such as plasma enhanced chemical vapor deposition. However, the vacuum deposition method is widely used as a highly productive process, but the gas barrier performance is inferior. Although a dense film can be formed by sputtering, the film formation rate is low and sufficient productivity cannot be obtained. Furthermore, since the film formed by the PVD method is inorganic and brittle, defects and peeling are likely to occur, and high barrier properties cannot be imparted.
On the other hand, the plasma CVD method has an advantage in terms of productivity as compared with the sputtering method, and can form a film having good gas barrier performance as compared with the vacuum evaporation method and the sputtering method.

Thus, the plasma CVD method can be preferably used as a method for forming the adhesion layer and the gas barrier layer. More preferably, a roll-to-roll type plasma CVD method can be used in terms of productivity and quality stability.
In CVD (Chemical Vapor Deposition), one or more source gases of a compound containing constituent elements of a thin film material to be manufactured are supplied onto a film formation target (for example, a substrate), and the vapor phase or the surface of the substrate is supplied. This is a method for producing a thin film by the chemical reaction. The plasma CVD method is a method in which a film forming gas is brought into a plasma state, active radicals and ions are generated, and a chemical reaction is performed in an active environment. In addition, as shown in FIG. 5, the roll-to-roll means that a film-forming target wound in a roll shape is sent out from a sending-out roll 31, and a target substance is formed and printed on the surface, and another roll (winding-up) is again made. This is a production method in which the take-up roll 32) is wound up and collected. The roller 33 is for conveying a film.

There are various types of film forming apparatuses using the plasma CVD method, but the film forming apparatus is not limited as long as the object of the present invention is not impaired.
For example, Japanese Patent Publication No. 2005-504880 includes a pair of film forming rolls that wind and convey a film to be formed, forms a magnetic field across the rolls, and the two film forming rolls are the same. It is connected to a high-frequency power source so as to be polar, and simultaneously, high-frequency power of several tens to several hundreds of kHz is supplied, and Benning discharge is generated in the opposing space (discharge region) between the rolls to confine plasma and oxygen in the opposing space And a material gas such as hexamethyldisiloxane (HMDSO) is supplied to form a film on a film on a film forming roll on both sides of the discharge region at the same time.

Japanese Patent No. 2587507 discloses a pair of film forming rolls (metal drums) arranged facing each other in a vacuum chamber, an AC power source in which one and the other electrode are connected to one and the other film forming rolls, respectively. A plasma CVD film forming apparatus having a discharge chamber disposed in an opposing space between film forming rolls and having a surface facing the film forming roll opened, and a monomer (raw material) gas supply means connected to the discharge chamber is described. Has been.

Further, in Japanese Patent No. 4268195, a pulse voltage accompanied by alternating current or polarity reversal is applied to the film forming rolls arranged to face each other under reduced pressure, and a facing space (film forming zone) between the film forming rolls arranged opposite to each other. ) Describes a device for generating a film by plasma CVD on a belt-like base material wound around facing a facing space of a film forming roll.
As an example, a plasma CVD apparatus (Roll coater W35) manufactured by Kobe Steel, Ltd. can be preferably used.

Examples of the metal oxide that is a main component of the adhesion layer and the gas barrier layer include silicon oxide, aluminum oxide, titanium oxide, and zinc oxide. Examples of the metal nitride include silicon nitride, aluminum nitride, titanium nitride, and zinc nitride. In applications where transparency is required for the gas barrier film laminate, silicon oxide is more preferable.

The source gas used for forming the adhesion layer and the gas barrier layer is preferably an organometallic compound. For example, an organosilicon compound containing silicon, an organoaluminum compound containing aluminum, or the like can be used. Among these source gases, it is more preferable to use an organosilicon compound from the viewpoints of handling properties of the compound and imparting flexibility and high gas barrier properties to the obtained adhesion layer and gas barrier layer.
Examples of organosilicon compounds include HMDSO, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyl Examples include triethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane, and hexamethyldisilazane.
Among these organosilicon compounds, HMDSO, 1,1,3,3-tetramethyldisiloxane, tetraethoxysilane, hexamethyldisilane are used from the viewpoint of characteristics such as handling of the compound and gas barrier properties of the obtained thin film layer. Silazane is particularly preferred.
These raw materials such as organosilicon compounds can be used singly or in combination of two or more.
Examples of the organoaluminum compound include trimethylaluminum.

In addition to the source gas, a reactive gas can be used. The reactive gases, e.g., oxygen _(O 2), ozone _(O 3), nitrogen monoxide (NO), nitrous oxide _(N 2 O), nitrogen dioxide _(NO 2), hydrogen peroxide _{(H 2} Oxidizing gas such as O ₂ ) and nitride forming gas such as nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), dimethyl hydrazine (N ₂ H ₂ (CH ₃ ) ₂ ) Can be used. These reactive gases can be used alone or in combination of two or more.

A carrier gas may be used as necessary for supplying the source gas into the vacuum chamber as a film forming gas. Furthermore, as a gas for film formation, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, xenon, and the like can be used.
In the present invention, the reactive gas may be used as a discharge gas. Reactive gas and noble gas can be used alone or in combination of two or more.

Such gas for film formation (gas used for film formation such as source gas, reactive gas, carrier gas, discharge gas, etc.) is collectively referred to as “film formation gas”.

The adhesion layer is preferably formed with a reactive gas mixture ratio higher than the reactive gas mixture ratio in the film forming gas when forming the gas barrier layer. Specifically, the mixing ratio of the reactive gas in the film forming gas when forming the adhesion layer is 1.2 to the mixing ratio of the reactive gas in the film forming gas when forming the gas barrier layer. It is preferably 4.0 times. More preferably, it is 1.5 to 3.0 times, and particularly preferably 1.8 to 2.7 times. When the ratio is 1.2 to 4.0 times, an adhesion layer having an appropriate elemental composition for expressing adhesion can be formed.

The pressure (degree of vacuum) in the vacuum chamber of the plasma CVD apparatus can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.1 Pa to 50 Pa.

The electric power applied for discharging can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.2 to 10 kW. When the applied power is equal to or higher than the lower limit, the reaction of the source gas is not insufficient and the barrier property is not lowered. As a result, wrinkles are not generated on the film formation target, and irregularities are not generated on the film surface and the appearance is not impaired.

The conveyance speed of the film formation target can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.1 to 50 m / min, preferably 0.3 to 20 m. / Min is more preferable. When the line speed is equal to or higher than the lower limit, wrinkles due to heat tend not to occur in the resin film being conveyed. When the line speed is equal to or lower than the upper limit, the thickness of the formed thin film layer does not become too thin.

The adhesion layer and the gas barrier layer contain an organic component. For example, when a thin film is formed by a plasma CVD method from a film forming gas (a mixed gas of HMDSO as a source gas and oxygen gas as an oxidizing gas (also functioning as a discharge gas)) and a gas barrier layer is formed, the following reaction formula is obtained. As described in (1), the formed film contains Cy (a trace amount of carbon component) as an organic component.
(CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₃ + O ₂ → SiO _x C _y (1)

As an example, when the adhesion layer and the gas barrier layer are formed by plasma CVD using HMDSO as a source gas and oxygen gas as an oxidizing gas, the adhesion layer satisfies a composition satisfying 1.8 <x <2.2. It is preferable to contain a compound containing SiO _x or containing a compound containing SiCy in the composition satisfying 0 <y <0.15. More preferably, 1.7 <x <2.1 or 0.02 <y <0.13. An adhesion layer satisfying such a composition ratio is preferable because it exhibits excellent adhesion.
Gas barrier layer satisfies 1.1 ≦ x ≦ 1.9,0 ≦ y ≦ 0.9, preferably contains a compound containing a _SiO x _{C y} in the composition. More preferably, 1.3 ≦ x ≦ 1.7 and 0 ≦ y ≦ 0.7. A gas barrier layer satisfying such a composition ratio is preferable because it exhibits excellent gas barrier properties.
For reference, FIG. 6 shows an XPS depth profile in which etching is started from the surface of the gas barrier layer of the adhesion layer and the gas barrier layer formed by plasma CVD using HMDSO as the source gas and oxygen gas as the oxidizing gas. The horizontal axis represents the etching time (minutes), and the vertical axis represents the atomic number concentration (%).
As shown in FIG. 6, the adhesion layer contains a compound containing SiO _{x in} which the composition ratio changes within a range of 1.8 <x <2.2, or the composition ratio is 0 <y <0.15. comprising a compound containing SiC _y varying in the range. The gas barrier layer contains a compound containing SiO _x C _y whose composition ratio changes in the range of 1.1 ≦ x ≦ 1.9 and 0 ≦ y ≦ 0.9.

[Gas barrier film laminate 10 ′]
A gas barrier film laminate 10 ′ according to the second embodiment of the present invention is formed on at least one side of a resin film 11 as a substrate and the resin film 11, for example, as shown in FIG. An organic film layer 12 is provided between the contact layer 13 and the contact layer 13.

[Organic film layer 12]
By providing an organic film layer on the gas barrier film laminate, the unevenness of the substrate surface is flattened, and curling of the gas barrier film laminate caused by residual stress generated during the film formation process of the adhesion layer and the gas barrier layer is suppressed. be able to. Therefore, the gas barrier film laminate can exhibit good processability. In addition, since cracks and film peeling due to curling are suppressed, good gas barrier properties can be maintained.

The thickness of the organic film layer is preferably 1 to 20 μm, more preferably 1.2 to 10 μm, still more preferably 2 to 8 μm. By setting the thickness to 1 μm or more, sufficient smoothness can be ensured and curling can be suppressed. Moreover, by setting it as 20 micrometers or less, while becoming easy to prevent the crack by bending, it becomes easy to adjust the balance of the optical characteristic of a gas barrier film laminated body.

The surface roughness of the organic film layer is preferably such that the arithmetic average roughness Sa is 5 nm or less, more preferably 3 nm or less, and even more preferably 2 nm or less. By setting the thickness to 5 nm or less, the adhesion layer and the gas barrier layer of the thin film laminated on the organic film layer can be uniformly treated, and the barrier property of the gas barrier film laminate is improved.

The organic film layer of the present invention is preferably a film obtained by photopolymerizing a photocurable resin composition. The photocurable resin composition is preferably composed of a composition containing an acrylic resin. The “photocurable resin composition” may be a composition that is photocured as a whole, and the photocurable resin does not necessarily have to be a main component.

Examples of the photocurable resin that is a precursor of the organic film layer include acrylic resins that can be cured by light such as ultraviolet irradiation. Examples thereof include resins having an unsaturated bond capable of radical polymerization, such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins. . These acrylic resins can be used alone or in admixture of two or more. Among them, polyester (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylate monomer and the like alone or a mixture thereof are preferable.
When an acrylic resin is used, an organic film layer excellent in transparency can be formed. Furthermore, an acrylic resin having photocurability is preferable because it has excellent curl prevention properties due to its hardness.

Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a silsesquioxane skeleton and has a (meth) acrylate group in a functional group is also mentioned.

As said unsaturated polyester resin, the condensation product (unsaturated polyester) by esterification reaction of a polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as needed) was melt | dissolved in the polymerizable monomer. Things.
The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane Polyhydric alcohols such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as alcohol components, and phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond or a polybasic acid anhydrides may include those prepared by adding as an acid component.

As the polyester (meth) acrylate resin, (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an α, β-unsaturated carboxylic ester group. (Meth) acrylate obtained by reacting an epoxy compound, (2) obtained by reacting a hydroxyl group-containing acrylate with a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or unsaturated polybasic acid and a polyhydric alcohol (Meth) acrylates obtained, (3) (meth) acrylates obtained by reacting (meth) acrylic acid with polyesters of terminal hydroxyl groups obtained from saturated polybasic acids and / or unsaturated polybasic acids and polyhydric alcohols It is done.
Examples of the saturated polybasic acid used as a raw material for polyester (meth) acrylate include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Further, the polyhydric alcohol component is the same as the unsaturated polyester.

The epoxy (meth) acrylate resin includes a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound having a compound (vinyl ester) dissolved in a polymerizable monomer.
The vinyl ester is produced by a known method, and includes an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
Further, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.

As the urethane (meth) acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.
Specific examples of polyisocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenyl. Methane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the polyhydroxy compound include polyester polyol and polyether polyol. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, tri Methylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene Examples include oxide adducts.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane. Diol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4- Examples include cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, and 2,7-decalin glycol.
The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specific examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) An acrylate etc. are mentioned.

The photocurable resin composition contains a photopolymerization initiator. As a specific example of a photoinitiator, if it is a compound which generate | occur | produces a radical by irradiation of an ultraviolet-ray or visible light, it will not specifically limit. Compounds used as photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) Benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichlorome ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2 , 6-Di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 '-Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7- Diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl- 2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η5-2,4-cyclope) Tajien-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanium, and the like. 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone is preferred.
The amount of the polymerization initiator used in the above addition polymerization is preferably about 0.01 to 10 mol% based on the total number of moles of monomers. These photopolymerization initiators can be used alone or in combination of two or more.

In the addition polymerization, a chain transfer agent may be used. The molecular weight can be appropriately controlled by using the chain transfer agent. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; and the like, toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, diethyl ketone, chloroform, ethylbenzene, butyl chloride, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloride Pyrene, methyl chloroform, t- butyl benzene, butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, tetrachloroethane, chlorobenzene, cyclohexane, t- butyl alcohol, benzene and the like. In particular, mercaptoacetic acid can lower the molecular weight of the polymer and make the molecular weight distribution uniform. These chain transfer agents can be used alone or in admixture of two or more.

Solvents used when preparing a coating solution in which a photocurable resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, α- or β- Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether Ter, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate Diethylene glycol dialkyl ether, dipropy Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide. These solvents can be used alone or in admixture of two or more.

A coating solution in which a photocurable resin is dissolved or dispersed in a solvent improves the surface fluidity and leveling properties of the coated coating solution and prevents pinholes and defects in the coating film due to poor wetting and repelling. Surface conditioning agents (leveling agents, wettability improvers, surfactants, etc.) may be included. Examples of the surface conditioner include polysiloxane, polyacrylate and wax.
In addition, an additive such as an antifoaming agent for preventing the generation of bubbles in the coating solution may be used. Examples of antifoaming agents include mineral oil compounds and polysiloxane compounds.
Furthermore, you may contain additives, such as a plasticizer, a ultraviolet absorber, antioxidant, and a silane coupling agent, as needed.

The method for forming the organic film layer is not particularly limited, but it is preferable to use a wet coating method (coating method) in order to uniformly coat the photocurable resin composition. By using the coating method, excellent surface smoothness can be obtained. Among the coating methods, when a small amount is prepared, a spin coating method capable of simple and uniform film formation is preferable. In the case of roll-to-roll, where productivity is important, gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coating method, a curtain coating method, a rod coating method and the like are preferable. The coating method can be appropriately selected from these methods according to the required film thickness, viscosity, curing conditions, and the like.

The applied coating solution can be dried with hot air or the like in an environment of room temperature to about 200 ° C. After the coating and drying, a photoactive energy beam or an electron beam is irradiated and cured by an active energy beam source. Although there is no particular limitation as a photoactive energy ray source, depending on the nature of the photopolymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser, An electron beam irradiation apparatus etc. are mentioned.
The drying furnace passage time for drying differs depending on the line speed, the type of coating liquid, the coating thickness, and the apparatus capacity (air volume, area, etc.). For example, 1 to 105 minutes can be mentioned. Similarly, the amount of irradiation for curing varies depending on the material and thickness. For example, when a high-pressure mercury lamp is used, about 200 to 700 mJ / cm ² can be mentioned.

The surface (resin film surface, organic film layer surface, gas barrier layer surface) of the gas barrier film laminate of the present invention may be subjected to surface modification treatment such as corona treatment or plasma treatment for the purpose of improving adhesion.

The gas barrier film laminate of the present invention has, for example, an adhesion layer 13 and a gas barrier layer 14 on at least one surface of the resin film 11 (FIG. 1A). Or it has the organic film layer 12, the contact | adherence layer 13, and the gas barrier layer 14 in the at least single side | surface of the resin film 11 (FIG.1 (b)). Preferably, the adhesion layer 13 and the gas barrier layer 14 are in contact with each other. More preferably, the resin film 11 and the organic film layer 12 are in contact with each other.
In the gas barrier film laminate of the present invention, the order of the layers laminated on the resin film is resin film / adhesion layer / gas barrier layer or resin film / organic film layer / adhesion layer / gas barrier layer, and the adhesion layer is provided. It improves the adhesion of the gas barrier layer.
In addition, as shown in FIGS. 1 (a) and 1 (b), the gas barrier layer has a structure in which the gas barrier layer is laminated only on one side of the resin film. It is preferable because the weight can be reduced, the light transmittance can be improved, and the manufacturing process can be simplified.

The gas barrier film laminate of the present invention exhibits a high gas barrier property with a water vapor transmission rate (temperature: 40 ± 0.5 ° C., relative humidity: 90 ± 5% RH) of 0.005 g / m ² / day or less. Unable to express less 0.001g ^/ m 2 ^/ day by optimizing the film forming conditions or the like, an organic film layer, the adhesion layer, by optimizing the thickness of the gas barrier layer, 0.0001 g ^{/ m} 2 / Day or less is achieved.

When the gas barrier film laminate of the present invention is used for a photoelectric element, an OLED element, an OPV element or the like, it is preferably composed only of a transparent material. The total light transmittance measured according to the JIS 7105 method is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
However, when it is desired to block transmission of visible light or ultraviolet light, or when transparency is not so required, an opaque gas barrier film laminate may be produced.

By providing the organic film layer, the gas barrier film laminate of the present invention suppresses as much as possible the internal stress that tends to curl in the use environment, and exhibits good anti-curl properties. Thereby, after manufacturing the said gas barrier film laminated body, when passing through other processes, such as an assembly process to a device, favorable workability is exhibited. Further, there is no crack or film peeling due to curling, and good gas barrier properties can be maintained.
For example, the gas barrier film laminate of the present invention formed by laminating on a PET film having a thickness of 125 μm is cut into 100 mm × 100 mm, placed on a surface plate, and fixed using a height measuring instrument such as a ruler. When the average value of the height of curled portions from the board surface (distance from the surface of the surface board) is “curl height”, the curl height is preferably 15 mm or less, more preferably 10 mm or less. Especially preferably, it is 5 mm or less. The “curl height” is an average of the heights of the four corners of a square film.

The gas barrier film laminate of the present invention can be used for applications that require blocking of various gases such as water vapor and oxygen. Particularly preferably, it can be usefully used for blocking various gases of an electronic element such as an OLED element or an OPV element. Moreover, when a gas barrier film laminated body is transparent, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side. Further, when used in an OLED element, light emission from the element is not hindered, so that the light emission efficiency is not deteriorated.

FIG. 2A shows a schematic diagram of an electronic component having the OLED element 22 in a solid sealing system. An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on a glass substrate 21, and the OLED element 22 is entirely covered with a solid sealing agent 23. In the electronic component having such a configuration, the gas barrier film laminate 10 of the present application can be used in place of the glass substrate 21 as shown in FIG.
Or as shown in FIG. 3, it is good also as a sandwich structure which pinched | interposed OLED element 22 with the gas barrier film laminated body 10 of this application. In that case, the gas barrier film laminate 10 may be adhered by the adhesive 25.

FIG. 4A shows a schematic diagram of an electronic component having an OLED element with a conventional hollow structure. An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on the glass substrate 21 and covered with a glass sealing material 28 that is present at a distance. The glass substrate 21 and the glass sealing material 28 are bonded (sealed) with an adhesive 25 on both sides. A getter 26 such as calcium oxide that adsorbs moisture is disposed inside the hollow, and is filled with N ₂ gas 27. In the conventional electronic component having such a configuration, as shown in FIG. 4B, the gas barrier film laminate 10 of the present application can be used as an alternative to the glass substrate 21 and the glass sealing material 28.
2 to 4, a gas barrier film laminate 10 ′ may be used in place of the gas barrier film laminate 10.

Also in an OPV element having positive and negative electrodes and a semiconductor material sandwiched between the positive and negative electrodes, the gas barrier film laminate of the present application can be similarly used as an alternative to a glass substrate.

As described above, when the gas barrier film laminate of the present invention is used as a transparent substrate for OLED elements, OPV elements, liquid crystal elements, etc., it is possible to meet the demands for weight reduction and size increase. Furthermore, roll-to-roll (feeding a substrate such as a resin film wound in a roll shape, processing the target substance on the surface of the substrate, etc., and then winding it up again to collect it In place of glass substrates that are heavy, easy to break, and difficult to increase in area. Can be satisfied.
Conventionally, film base materials such as transparent plastics have a problem that gas barrier properties are inferior to glass, but when the gas barrier film laminate of the present invention is used, for example, electronic components such as OLED elements and OPV elements When used as a material, the substrate having excellent gas barrier properties can prevent water (water vapor) or oxygen from permeating and degrading components constituting the device, thereby reducing performance.

As described above, the present invention mainly includes electronic elements such as organic electroluminescent elements (OLED elements) and display elements typified by liquid crystal elements, photoelectric elements typified by organic solar cell elements (OPV elements), or OLED elements. It is a gas barrier film laminate that can be used for products such as lighting. The gas barrier film laminate of the present invention is characterized by excellent gas barrier layer adhesion, good productivity, low curl, and good gas barrier properties.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the contents described in the following examples.

<Measurement of film thickness of gas barrier layer>
Using a scanning electron microscope (SEM), the tomographic plane of the gas barrier film laminate was observed under the following conditions, and the total thickness of the adhesion layer and the gas barrier layer and the thickness of the gas barrier layer were measured.
・ SEM observation equipment: SU-70 manufactured by Hitachi, Ltd.
Acceleration voltage: 10 kV

<Measurement of adhesion>
The produced gas barrier film laminate was cut into a 10 cm square, attached to a stainless steel frame, stored at a temperature of 85 ° C. and a humidity of 85%, and the time until the gas barrier layer was peeled off (adhesion) was measured.

<Measurement of water vapor transmission rate (WVTR)>
The method for measuring the water vapor transmission rate is not particularly limited, but metallic calcium is vapor-deposited on one side of the gas barrier film laminate, Ca is sealed with Al and wax, and the metallic Ca is corroded by moisture that has passed through the film. A method using the phenomenon was used. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area. In the present invention, the evaluation was performed by the method described in Japanese Patent No. 3958235 and the following conditions.
-Ca method used for evaluation of the present invention Vapor deposition apparatus: manufactured by Sanyu Electronics Co., Ltd., electron beam vacuum deposition apparatus SVC-700LEB
Constant temperature and humidity chamber: Espec Co., Ltd., constant temperature and humidity chamber LHL-113
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal for Ca sealing: Aluminum (φ3-5mm, granular)
Sealing material: mixture of paraffin (melting point 60-62 ° C) / beeswax (melting point 61-65 ° C) in a weight ratio of 1: 1 Observation device: Calcium corrosion observation device MFB-1000 manufactured by Mitsuwa Frontec Co., Ltd.

<Measurement of X-ray photoelectron spectroscopy (XPS)>
The obtained gas barrier film laminate, carried out XPS depth profile measurement under the following conditions to obtain a silicon distribution curve, oxygen distribution curve, the carbon distribution curve, and the SiO ₂ equivalent thickness from the etching time.
Equipment: PHI Quantera SXM (ULVAC-PHI)
Irradiation X-ray: Monochromatic AlKα
X-ray beam diameter and output: Diameter 100 μm, 15 KV, 25 W
Argon etching analysis: Etching rate 20 nm / min. (SiO ₂ conversion)

<Example 1>
・ Base material As a base material, a polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.) wound in a roll shape with a thickness of 125 μm and a width of 550 mm, which is easily bonded on both sides. Using.

Preparation of coating solution for photocurable resin composition Unidic V-6841 (trade name, (meth) acrylate polymer / acrylate monomer / methyl isobutyl ketone = 25 to 35 parts by weight / 25 to 35 parts by weight / 35 to 45 parts by weight of a mixture, DIC Corporation UV curable coating agent): 55 parts by weight Methyl ethyl ketone (Wako Pure Chemical Industries, Ltd. solvent): 43 parts by weight IC184 (trade name, photopolymerization initiator manufactured by BASF) : 2 parts by weight were prepared.

-Deposition of organic film layer Using a roll-to-roll gravure coater, the coating solution is applied on the substrate so that the average film thickness after drying is 5 µm, and then the temperature is 85 ° C and the air volume is Drying was performed at 20 m / second and a residence time in the drying furnace of 50 seconds. Thereafter, photocuring was performed at a dose of 300 mJ / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere to form an organic film layer.

・ Formation of adhesion layer Using the plasma CVD apparatus (model number W35 type) PE-CVD manufactured by Kobe Steel Co., Ltd., which can be formed by roll-to-roll on the surface of the base material treated with the organic film layer. Thus, an adhesion layer was formed.
Under the conditions shown below, plasma is generated between the discharge electrodes, and in this discharge region, a film forming gas (mixed gas of HMDSO as a source gas and oxygen gas as an oxidizing gas (also functions as a discharge gas)) Was supplied, and a thin film was formed by a plasma CVD method according to the method described in JP-A-2012-81632 to obtain an adhesion layer having a SiO ₂ equivalent film thickness of 140 nm.
The adhesion layer was produced under the following conditions.
Source gas: HMDSO (manufactured by AZMAX Co., Ltd., trade name “SIH6115.0”)
Supply amount 50sccm
Oxidizing gas: Oxygen gas (manufactured by Suzuki Shokan Co., Ltd., high-purity oxygen, purity ≧ 99.999%)
Supply amount 1000sccm
Pressure 3Pa
Plasma power 1.3 kW
Substrate conveyance speed 1.0 m / min.

-Gas barrier layer deposition A gas barrier layer was deposited under the same plasma deposition apparatus and deposition conditions as those for the adhesion layer except that oxygen gas was changed to 500 SCCM under the deposition conditions in the plasma CVD method.
The laminated gas barrier layer has a SiO ₂ equivalent film thickness of 560 nm.
The total SEM film thickness of the adhesion layer and the gas barrier layer is 861 nm.
<Example 2>
-Base material Polyethylene naphthalate (PEN) film (trade name “Q65HA”, manufactured by Teijin DuPont Films, Inc.) rolled into a roll with a thickness of 125 μm and a width of 550 mm that is easily bonded to one side as a base material Was used.
Other than this, it was produced in the same manner as the preparation of the coating solution of the photocurable resin composition of Example 1, the formation of the organic film layer, the formation of the adhesion layer, and the formation of the gas barrier layer.
The laminated gas barrier layer has a SiO ₂ equivalent film thickness of 590 nm.
The total SEM film thickness of the adhesion layer and the gas barrier layer is 946 nm.

<Comparative Example 1>
Comparative Example 1, the adhesion layer is not present, the thickness of the gas barrier layer is a 700nm of SiO ₂ equivalent thickness, except treated so as to 917nm by SEM film thickness, substrate of Example 1, The photocurable resin composition was prepared in the same manner as in the preparation of the coating solution, the organic film layer, and the gas barrier layer.
<Comparative example 2>
-Base material As a base material, a polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) wound in a roll shape with a thickness of 125 μm and a width of 550 mm that is easily bonded on one side. Using.
-Gas barrier layer film formation A plasma film formation apparatus and film formation similar to those of the gas barrier layer of Example 1 except that the plasma power was set to 0.9 kW under the film formation conditions by the plasma CVD method on the substrate. A gas barrier layer was formed under film conditions.
The laminated gas barrier layer has a SiO ₂ equivalent film thickness of 690 nm.
The SEM film thickness is 926 nm.
In Comparative Example 2, the adhesion layer was not present, and the film thickness of the gas barrier layer was 690 nm in terms of SiO ₂ , and the SEM film thickness was 926 nm. Preparation of the coating solution of the photocurable resin composition and film formation of the organic film layer were produced in the same manner as in Example 1.

FIG. 6 shows an XPS depth profile of the first embodiment. The etching time of 0 to about 28 minutes indicates the atomic number concentration of the gas barrier layer, and about 28 minutes to about 35 minutes indicates the atomic number concentration of the adhesion layer. After about 35 minutes, the atomic number concentration of the organic film layer is obtained.
FIG. 7 shows an XPS depth profile of the second embodiment. When the etching time is from 0 to about 26 minutes, the atomic number concentration of the gas barrier layer is shown, and from about 26 minutes to about 32 minutes, the atomic number concentration of the adhesion layer is shown. After about 32 minutes, the concentration is the number of atoms in the organic film layer.
FIG. 8 shows an XPS depth profile of Comparative Example 1. The etching time from 0 to about 35 minutes is the atomic concentration of the gas barrier layer, and after about 35 minutes is the atomic concentration of the organic film layer.
FIG. 9 shows an XPS depth profile of Comparative Example 2. The etching time from 0 to about 45 minutes is the atomic concentration of the gas barrier layer, and after about 45 minutes is the atomic concentration of the organic film layer.

The measurement results are shown below.

As is apparent from Table 1, it can be seen that the gas barrier film laminate of the present invention has high barrier properties, and at the same time, the gas barrier layer exhibits excellent adhesion compared to Comparative Examples 1 and 2.

The present invention mainly relates to a gas barrier film laminate used for an electronic component having an electronic element such as an OLED element, an OPV element, or a liquid crystal element, and an electronic component including the gas barrier film laminate.

All publications, including publications, patent applications and patents cited herein are specifically incorporated by reference with reference to each reference individually, and the entire contents thereof are described herein. To the same extent, reference here is incorporated.

The use of nouns and similar directives used in connection with the description of the invention (especially in connection with the claims below) is not specifically pointed out herein or clearly contradicted by context. , And construed to cover both singular and plural. The phrases “comprising”, “having”, “including” and “including” are to be interpreted as open-ended terms (ie, including but not limited to) unless otherwise specified. The use of numerical ranges in this specification is intended only to serve as a shorthand for referring individually to each value falling within that range, unless otherwise indicated herein. Each value is incorporated into the specification as if it were individually listed herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any examples or exemplary phrases used herein (eg, “etc.”) are intended only to better describe the invention, unless otherwise stated, and to limit the scope of the invention. is not. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

In this specification, preferred embodiments of the present invention are described, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art after reading the above description. The inventor anticipates that skilled artisans will apply such variations as appropriate and intends to implement the invention in ways other than those specifically described herein. . Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

10, 10 ′ Gas barrier film laminate 11 Resin film 12 Organic film layer 13 Adhesion layer 14 Gas barrier layer 21 Glass substrate 22 Electronic element, OLED element 23 Solid sealant 25 Adhesive 26 Getter 27 N ₂ gas 28 Glass sealant 31 Feeding roll 32 Winding roll 33 Roller

Claims

A resin film as a substrate;
Formed on at least one side of the resin film, satisfying 1.8 <x <2.2, an adhesion layer containing a compound containing SiO x in the composition, or satisfying 0 <y <0.15, An adhesion layer containing a compound containing SiC y in the composition;
Said deposited on the adhesion layer, satisfy 1.1 ≦ x ≦ 1.9,0 ≦ y ≦ 0.9, and a gas barrier layer containing a compound containing SiO x C y in the composition;
Gas barrier film laminate.
The adhesion layer has a thickness of 10 to 500 nm.
The gas barrier film laminate according to claim 1.
The adhesion layer and the gas barrier layer are continuously formed by a plasma CVD method,
The ratio of the reactive gas in the film forming gas at the time of forming the adhesion layer is larger than the ratio of the reactive gas in the film forming gas at the time of forming the gas barrier layer.
The gas barrier film laminate according to claim 1 or 2.
The ratio of the reactive gas in the film forming gas at the time of forming the adhesion layer is 1.2 to 4.0 times the ratio of the reactive gas in the film forming gas at the time of forming the gas barrier layer.
The gas barrier film laminate according to claim 3.
The resin film is a film mainly composed of a resin that is polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof.
The gas barrier film laminate according to any one of claims 1 to 4.
The water vapor transmission rate at 40 ° C. and 90% RH is 0.005 g / m 2 / day or less,
The gas barrier film laminate according to any one of claims 1 to 5.
An organic film layer sandwiched between the resin film and the adhesion layer;
The gas barrier film laminate according to any one of claims 1 to 6.
The organic film layer is a layer obtained by photopolymerizing a photocurable resin composition.
The gas barrier film laminate according to claim 7.
An electronic device having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes;
The gas barrier film laminate according to any one of claims 1 to 8, which protects the electronic element from water vapor;
Electronic components.
The gas barrier film laminate is transparent,
The electronic element is an OLED element or an OPV element;
The electronic component according to claim 9.