TW201709586A - Gas barrier film, transfer printing method for gas barrier film, wavelength conversion film, phase difference film having gas barrier layer, and organic EL laminated body having a higher gas barrier property after transfer printing - Google Patents

Abstract

The invention provides a gas barrier film and a transfer printing method for the gas barrier film that is thinner and suitable for transfer printing and has a higher gas barrier property after the transfer printing, and the invention provides a wavelength conversion film using the gas barrier film, a phase difference film having a gas barrier layer and an organic EL laminated body. The gas barrier film has: a substrate; a gas barrier layer disposed on a surface of the substrate and having more than one set of compositions of inorganic layers and organic layers becoming the formation surfaces of the inorganic layers; and a peeling resin layer disposed between the substrate and the gas barrier layer to adhere to the organic layers and be peeled from the substrate.

Description

Gas barrier film, gas barrier film transfer method, wavelength conversion film, retardation film with gas barrier layer, and organic EL laminate

The present invention relates to a method for transferring a gas barrier film and a gas barrier film, and a wavelength conversion film using the gas barrier film, a retardation film having a gas barrier layer, and an organic EL laminate.

In recent years, high resistance is required in packaging materials such as organic EL devices (organic electroluminescence devices), solar cells, quantum dot films, and the like, and packaging materials such as infusion bags that contain agents that are degraded by moisture or oxygen. Gas. Thereby, a gas barrier film is attached to the members in order to impart necessary gas barrier properties, or is sealed by a gas barrier film.

In order to apply a gas barrier film to a field requiring high gas barrier properties, Patent Document 1 discloses a method for improving gas barrier properties as follows: a structure in which an inorganic layer is used as a gas barrier layer; and a gas barrier layer is multilayered. a structure; and forming a gas barrier layer in the resin film having a high glass transition temperature Tg.

Gas barrier films with high gas barrier properties have been developed into a variety of electronic devices or functional films, and are capable of sealing materials that were previously difficult to seal. For example, Patent Document 2 discloses that a quantum dot film used as a backlight unit for an LCD or the like has a quantum dot layer (a QD phosphor material thin film layer) sandwiched between two gas barrier films, thereby performing quantum dots. Protected laminated quantum dot film. Further, Patent Document 3 describes a case where an organic EL element is sealed with a gas barrier film.

By using a gas barrier film having a high gas barrier property, it is possible to reduce the thickness, weight, and flexibility of a plurality of types of electronic devices such as displays. Therefore, if the gas barrier film can be further reduced in thickness, it is possible to further reduce the thickness and weight of the electronic device. As described in Patent Document 1 and the like, such a gas barrier film has a structure in which a resin film is used as a substrate, and a gas barrier layer is formed on the substrate. Therefore, it is conceivable to make the substrate thinner when the gas barrier film is made thinner. Here, the gas barrier layer having a higher gas barrier property is a thinner inorganic layer. Therefore, the gas barrier layer is easily broken even in a slight buckling or contact, and the performance is lowered if it is broken. Therefore, when the gas barrier layer is laminated on the thin substrate, it is necessary to stabilize the transfer so that the substrate can be prevented from being buckled.

Patent Document 4 discloses that a protective material is attached to the back surface side of the substrate, whereby the self-supporting property of the substrate can be ensured, and when a thin substrate is used, the gas barrier layer can be appropriately formed without being formed. The buckling of the substrate is produced. According to this method, a gas barrier layer can be formed on a thin substrate of about 10 μm. However, when the substrate is made thinner, it is more difficult to bond the reinforcing protective material to the substrate while transporting the thin substrate.

As a solution to the problem of the thinning of the gas barrier film, a transfer method in which only the gas barrier layer is transferred to the object to be sealed (the transfer target) has been proposed.

For example, Patent Document 5 describes that a release layer is formed between a substrate and a gas barrier layer, and the gas barrier layer is peeled off from the substrate and transferred to the transfer target. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-118564

As described above, in order to achieve high gas barrier properties, there is a structure in which an inorganic layer is used in the gas barrier layer. According to the research of the inventors of the present invention, as described in Patent Document 5, in the gas barrier film in which the gas barrier layer is peeled off from the substrate and transferred to the transfer target, there is a case where the gas barrier is caused. When the layer is peeled off from the substrate, the inorganic layer is easily broken by the shearing force due to the shearing force applied to the gas barrier layer, and the gas barrier layer after the transfer cannot exhibit sufficient gas barrier properties.

The object of the present invention is to solve the problems of the prior art, and to provide a transfer method of a gas barrier film and a gas barrier film which are thin and capable of being transferred, and which has a high gas barrier property after transfer, and further A wavelength conversion film using the gas barrier film, a retardation film having a gas barrier layer, and an organic EL laminate are provided.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a gas barrier layer having a substrate and a combination of one or more inorganic layers and an organic layer forming a surface of the inorganic layer is provided on one surface side of the substrate. And the peeling resin layer provided between the substrate and the gas barrier layer and adhered to the organic layer and used for peeling off the substrate and the gas barrier layer can solve the above problems, and completed the present invention. That is, the present invention provides a method for producing a gas barrier film and a gas barrier film having the following structure, and a wavelength conversion film using the gas barrier film, a retardation film having a gas barrier layer, and an organic EL laminate.

(1) A gas barrier film comprising: a substrate; a gas barrier layer provided on one surface side of the substrate, having a combination of one or more inorganic layers and an organic layer as a formation surface of the inorganic layer; and a release resin layer, It is disposed between the substrate and the gas barrier layer, adheres to the organic layer, and is used for peeling off the substrate and the gas barrier layer. (2) The gas barrier film according to (1), wherein the release resin layer is thicker than the organic layer. (3) The gas barrier film according to (1) or (2), wherein the material for forming the release resin layer is a cyclic olefin resin having a glass transition temperature Tg of 100 ° C or more. (4) The gas barrier film according to (3), wherein the material for forming the release resin layer is a cyclic olefin copolymer. (5) The gas barrier film according to any one of (1) to (4) wherein the peeling resin layer has a thickness of 0.1 to 25 μm. (6) The gas barrier film according to any one of (1) to (5) wherein the inorganic layer forming material is tantalum nitride, cerium oxide, or a mixture thereof. (7) The gas barrier film according to any one of (1) to (6) wherein the material for forming the organic layer is an ultraviolet curable resin or an electron beam curable resin, and the glass transition temperature Tg after curing is 200 ° C or higher. (8) The gas barrier film according to (7), wherein the organic layer forming material contains 5% or more and less than 50% of a monofunctional or higher acrylate having an adamantane skeleton. (9) The gas barrier film according to (7), wherein the organic layer forming material contains 5% or more and less than 50% of a bifunctional or higher acrylate having an anthracene skeleton. (10) The gas barrier film according to any one of (1) to (9) wherein the organic layer has a thickness of 0.1 to 5 μm. (11) The gas barrier film according to any one of (1) to (10), further comprising a protective film or an organic protective layer provided on the gas barrier layer. (12) The gas barrier film according to (11), wherein the organic protective layer is an acrylic adhesive. (13) The gas barrier film according to (11) or (12), further comprising a protective film provided on the organic protective layer. (14) The gas barrier film according to any one of (11) to (13) wherein the organic protective layer has a thickness of 0.1 to 50 μm. (15) The gas barrier film according to any one of (1) to (14) wherein the substrate is provided with a polyethylene terephthalate film of the release layer. (16) The gas barrier film according to any one of (1) to (15), wherein a structure in which the substrate is removed has a water vapor transmission rate of less than 0.01 g/(m ² day). The gas barrier film according to any one of (1) to (16), wherein the structure in which the substrate is removed has a visible light transmittance of 85% or more and a retardation value of 30 nm or less. (18) A method of transferring a gas barrier film, wherein a transfer layer having a gas barrier layer and a release resin layer is transferred to a transfer target, wherein the resistance according to any one of (1) to (17) is blocked The surface of the gas film opposite to the substrate is attached to the object to be transferred, and the substrate is peeled off. (19) The method of transferring a gas barrier film according to (18), wherein the wavelength conversion material, the retardation film, the organic EL element, and the passivation film formed on the organic EL element are transferred. (20) A wavelength conversion film comprising: a wavelength conversion layer; and a transfer layer laminated on the wavelength conversion layer, and having the gas barrier film according to any one of (1) to (17), wherein the substrate is removed A gas barrier layer and a release resin layer. (21) A retardation film having a gas barrier layer, comprising: a retardation film; and a transfer layer laminated on the retardation film, and having the gas barrier according to any one of (1) to (17) The film removes the gas barrier layer and the release resin layer of the substrate. (22) An organic EL laminate comprising: an organic EL device; and a transfer layer laminated on the organic EL device, and having the gas barrier film according to any one of (1) to (17), wherein the substrate is removed The gas barrier layer and the release resin layer. (23) The organic EL laminate according to (22), wherein a passivation film is provided between the organic EL element and the transfer layer. (24) The organic EL laminate according to (22), further comprising an element substrate supporting the organic EL element, the element substrate including a transfer layer having (1) to (17) The gas barrier film according to any one of the aspects removes the gas barrier layer and the release resin layer of the substrate.

According to the present invention, it is possible to provide a transfer method of a gas barrier film and a gas barrier film which are thin and capable of being transferred, and which has a high gas barrier property after transfer, and provide the gas barrier film. A wavelength conversion film, a retardation film with a gas barrier layer, and an organic EL laminate.

Hereinafter, the gas barrier film of the present invention will be described in detail based on the preferred embodiment shown in the drawings.

The gas barrier film of the present invention is a gas barrier film having: a substrate; a gas barrier layer disposed on one surface side of the substrate and having a plurality of inorganic layers and an organic surface forming the inorganic layer a combination of layers; and a release resin layer disposed between the substrate and the gas barrier layer, adhered to the organic layer, and used for peeling off from the substrate. This gas barrier film removes only the substrate and transfers the transfer layer including the gas barrier layer and the release resin layer to the user to be transferred.

An example of the gas barrier film of the present invention is schematically shown in Fig. 1(A). The gas barrier film 10a shown in FIG. 1(A) is basically constituted by having a substrate 12, a gas barrier layer 18 laminated on one surface of the substrate 12, and having an organic layer 14 and an inorganic layer 16 And the peeling resin layer 20 is laminated between the substrate 12 and the gas barrier layer 18. Further, as shown in FIG. 1(A), the organic layer 14 of the gas barrier layer 18 is laminated toward the release resin layer 20 side, and the inorganic layer 16 is laminated on the organic layer 14. That is, the release resin layer 20 is laminated between the substrate 12 and the organic layer 14.

Here, as shown in FIG. 1(B), in the gas barrier film 10a, the release resin layer 20 is configured to adhere to the organic layer 14, and is capable of being peeled off from the substrate 12 at the interface with the substrate 12. That is, the peeling force (adhesion force) between the organic layer 14 and the release resin layer 20 is larger than the peeling force between the substrate 12 and the release resin layer 20. Thereby, in the gas barrier film 10a, only the substrate 12 is peeled off, and the transfer layer 30 including the gas barrier layer 18 and the release resin layer 20 can be transferred to the object to be transferred as the object to be sealed. Further, when the transfer layer 30 is transferred to the transfer target, the gas barrier layer 18 side of the gas barrier film 10a is attached to the transfer target body, and the substrate 12 is peeled off from the gas barrier film 10a. Although the transfer layer 30 is transferred to the transfer target, the transfer layer 30 may be attached to the transfer target after the transfer layer 30 is taken out by peeling off the substrate 12 from the gas barrier film 10a.

As described above, as a thinner gas barrier film, a gas barrier film in which a release layer is formed between a substrate and a gas barrier layer, and a gas barrier layer is peeled off from the substrate to be transferred to the transfer target is proposed. However, according to the study by the present inventors, it is known that the gas barrier film of such a transfer method has a case where the shearing force is applied to the gas barrier layer by the shearing force when the gas barrier layer is peeled off from the substrate. The inorganic layer is easily broken, and the gas barrier layer after transfer cannot exhibit sufficient gas barrier properties.

On the other hand, the present invention has a structure in which the organic layer 14 is provided as a base for exhibiting the gas barrier inorganic layer 16, and a release resin layer 20 is provided between the organic layer 14 and the substrate 12, and the release resin layer 20 and the organic layer are provided. 14 adheres and is capable of peeling off from the substrate 12 at the interface with the substrate 12. At the time of peeling, the interface between the peeling resin layer 20 and the substrate 12 is peeled off, whereby the peeling resin layer 20 existing between the inorganic layer 16 and the peeling surface serves as a stress relieving layer, and the shear required for peeling off the substrate 12 can be prevented. The rupture of the inorganic layer 16 of the shear force.

Here, as described above, in the peeling of the resin layer 20, it is necessary to adjust the peeling force so as to peel off from the interface with the substrate 12, and it is necessary to have a function as a stress relieving layer. Therefore, it is not suitable as a base layer of the inorganic layer 16. In particular, in order to obtain the inorganic layer 16 having high gas barrier properties, it is required to have a suitable hardness as a layer of the substrate of the inorganic layer 16, and it is required to have high heat resistance. Therefore, in the case where the structure of the organic layer 14 is not provided between the release resin layer 20 and the inorganic layer 16, that is, in the case where the inorganic layer 16 is directly formed on the release resin layer 20, the inorganic layer 16 cannot be formed reasonably. And can not get a higher gas barrier.

On the other hand, in the gas barrier film of the present invention, since the organic layer 14 is provided on the release resin layer 20 as the formation surface of the inorganic layer 16, it has a preferable underlayer. Thereby, the inorganic layer 16 can be formed reasonably, and high gas barrier properties can be obtained.

Further, in the gas barrier film of the present invention, it is preferable to further provide a protective film for protecting the gas barrier layer 18 (more specifically, the inorganic layer 16) on the gas barrier layer 18. By having a protective film, it is possible to prevent the inorganic layer 16 from being broken when the gas barrier film is transferred or wound. Further, when the protective film is provided, the gas barrier film may be peeled off to expose the gas barrier layer 18, and then transferred to the object to be transferred.

Further, as the gas barrier film 10b shown in Fig. 2(A), it is also preferable to have the organic protective layer 24 for protecting the gas barrier layer 18 on the gas barrier layer 18 (more specifically, the inorganic layer 16). By having the organic protective layer 24, the inorganic layer 16 can be prevented from being broken when the gas barrier film is transferred or wound. Further, when the organic protective layer 24 is provided, the release resin layer 20, the gas barrier layer 18, and the organic protective layer 24 become the transfer layer 30, and the organic protective layer 24 is transferred together with the release resin layer 20 and the gas barrier layer 18 Transfer body.

Further, the organic protective layer 24 may be an adhesive layer having an adhesive property. When the organic protective layer 24 has adhesiveness and the transfer layer 30 is transferred to the transfer target, the transfer can be easily performed without applying the adhesive or the like.

Further, as the gas barrier film 10c shown in FIG. 2(B), the organic gas barrier layer 24 may be provided on the gas barrier layer 18, and the protective film 26 may be provided on the organic protective layer 24. By having the organic protective layer 24 and the protective film 26, it is possible to prevent the inorganic layer 16 from being broken when the gas barrier film is transferred or wound. Further, when the organic protective layer 24 is an adhesive layer, the gas barrier film can be easily transported or wound by the protective film 26, and impurities and the like can be prevented from adhering to the adhesive layer, and the adhesiveness can be prevented from being lowered.

Further, in the example shown in FIG. 1(A), the gas barrier layer 18 has a structure in which one organic layer 14 and one inorganic layer 16 are provided. However, the present invention is not limited thereto, and may have one or more organic layers. The layer and the inorganic layer may have a combination of two or more inorganic layers 16 and an organic layer 14 which is a base layer of the inorganic layer 16. For example, the gas barrier film 10d shown in FIG. 3 has the gas barrier layer 18 in which the organic layer 14, the inorganic layer 16, the organic layer 14, and the inorganic layer 16 are sequentially formed on the release resin layer 20. That is, the gas barrier layer 18 of the gas barrier film 10d has a structure in which two sets of the organic layer 14 and the inorganic layer 16 are combined. As described above, by combining two or more organic layers 14 and inorganic layers 16, the gas barrier properties can be further improved.

Here, the gas barrier film of the present invention in which the gas barrier film is removed from the water vapor transmission rate of the substrate structure 12 is less than ^{0.01 [g / (m 2 ·} day)] is preferred, of 0.005 [g / (m ²・day)] The following is more preferable, and it is particularly preferable that it is 0.001 [g/(m ²・day)] or less. For example, in the case where the gas barrier film is composed of the substrate 12, the gas barrier layer 18, and the release resin layer 20, the structure in which the substrate 12 is removed from the gas barrier film means that the gas barrier layer 18 and the release resin layer 20 are formed. Print layer 30. Further, in the case where the gas barrier film is composed of the substrate 12, the gas barrier layer 18, the release resin layer 20, and the organic protective layer 24, the structure for removing the substrate 12 from the gas barrier film means that the gas barrier layer 18 and the peeling resin layer are formed. 20. The transfer layer 30 formed of the organic protective layer 24. The gas barrier film of the present invention has a low water vapor transmission rate. In the gas barrier film of the present invention, even if the gas barrier property of the transfer layer 30 is high, the inorganic layer 16 can be prevented from being broken, and the transfer can be appropriately performed while maintaining high gas barrier properties.

Further, in the gas barrier film of the present invention, the visible light transmittance of the structure in which the substrate 12 is removed from the gas barrier film is preferably 85% or more. Further, the retardation value of the transfer layer 30 is preferably 30 nm or less. When the gas barrier film of the present invention is transferred by the transfer of the visible light transmittance and the retardation value of the transfer layer 30 to the above, the wavelength conversion layer such as a quantum dot film or an optical member such as an organic EL device is sealed, or When gas barrier properties are imparted to an optical film such as a retardation film, the optical member can be sealed or gas barrier properties can be imparted without affecting the optical properties of the transfer target.

Next, the materials, structures, and the like of the respective constituent elements of the gas barrier film of the present invention will be described. Hereinafter, the gas barrier films 10a to 10d are collectively referred to as "gas barrier film 10".

In the gas barrier film 10, the substrate 12 can be used as various known sheets which are used as a substrate (support) in various gas barrier films or various laminated gas barrier films.

Specifically, as the substrate 12, preferably, low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene naphthalate (PEN), polyamine (PA), poly Ethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyimine (PI), transparent polyimide, polymethacrylic acid Methyl ester resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), ABS, cyclic olefin copolymer (COC), cyclic olefin polymerization A film (resin film) composed of various resin materials such as COP and cellulose triacetate (TAC).

In the present invention, as the substrate 12, a protective layer, a bonding layer, a light reflecting layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, a stress relaxation layer, a release layer, and the like may be formed on the surface of such a film. The layer (film) of the necessary function.

Among them, the elongation at break is high, and it is not easy to be broken during transportation, and the thickness can be made thin, the melting point is high, and heat resistance can be easily performed at the interface with the release resin layer 20, and the price is low. It is considered that as the substrate 12, a PET film having a release layer formed thereon is preferable. More specifically, in the PET film, a release layer is preferably formed on the surface on which the release resin layer 20 is formed.

The thickness of the substrate 12 may be appropriately set depending on the use of the gas barrier film 10, the forming material, and the like. According to the study by the inventors of the present invention, the thickness of the substrate 12 is preferably 5 to 125 μm, more preferably 5 to 100 μm, and particularly preferably 10 to 50 μm. By setting the thickness of the substrate 12 to the above range, the mechanical strength of the gas barrier film 10 can be sufficiently ensured, and peeling can be easily performed at the time of transfer, which is preferable.

The organic layer 14 is a layer composed of an organic compound, and is substantially polymerized (crosslinked) to constitute a monomer or oligomer of the organic layer 14.

The organic layer 14 is a formation surface of the inorganic layer 16. Specifically, in the gas barrier film 10, the organic layer 14 functions mainly as a base layer for appropriately forming the inorganic layer 16 exhibiting gas barrier properties. By having such an organic layer 14, it is possible to embed the unevenness of the surface of the release resin layer 20 (or the inorganic layer 16 of the lower layer) or the foreign matter adhering to the surface of the release resin layer 20 (or the inorganic layer 16 of the lower layer). The surface on which the inorganic layer 16 is formed is in a state suitable for forming the inorganic layer 16 into a film. By this, it is possible to remove irregularities caused by the unevenness of the surface of the release resin layer 20 (or the inorganic layer 16 of the lower layer) or the adhesion of foreign matter, so that the inorganic compound forming the inorganic layer 16 is difficult to form a film, and the entire resin layer is peeled off. The surface of 20 (or the inorganic layer 16 of the lower layer) is formed into a film with a gap-free manner, and the inorganic layer 16 having a high gas barrier property can be formed.

Further, the glass transition temperature Tg of the organic layer 14 is preferably higher than the glass transition temperature Tg of the release resin layer 20, and is preferably 200 ° C or more. By setting the organic layer 14 having a high heat resistance such that the glass transition temperature Tg is 200 ° C or higher, the inorganic layer 16 can be formed into a film. Moreover, it is preferable that the organic layer 14 has appropriate flexibility in order to prevent cracking of the inorganic layer 16 or the like. Further, the glass transition temperature Tg may be measured in accordance with JIS K 7121.

In the gas barrier film 10, the material for forming the organic layer 14 is not limited, and various known organic compounds can be used. Specifically, a polyester, a (meth)acrylic resin, a methacrylic acid-maleic acid copolymer, a polystyrene, a transparent fluororesin, a polyimine, a fluorinated polyimine, or a fluorinated polyimide may be preferably exemplified. Polyamide, polyamine-imine, polyether oximine, cellulose oxime, polyurethane, polyetheretherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether oxime, polyfluorene A film of a thermoplastic resin such as an anthracene-modified polycarbonate, an alicyclic modified polycarbonate, an anthracene-modified polyester, an acrylic compound, a polyoxyalkylene or other organic hydrazine compound. They can be used in combination.

Among them, the organic layer 14 composed of a radical curable compound and/or a polymer of a cationically curable compound having an ether group in a functional group is preferable from the viewpoint of excellent glass transition temperature and strength. Among them, from the viewpoints of a lower refractive index, higher transparency, and excellent optical characteristics, as the organic layer 14, a monomer or oligomer of acrylate and/or methacrylate is particularly preferably exemplified. An acrylic resin or a methacrylic resin having a polymer as a main component. Among them, dipropylene glycol di(meth)acrylate (DPGDA), trimethylolpropane tri(meth)acrylate (TMPTA), dipentaerythritol hexa(meth)acrylate (DPHA) can be preferably exemplified. An acrylic resin or a methacrylic resin containing, as a main component, a polymer such as a monomer or oligomer of a acrylate or/or methacrylate having two or more functional groups, particularly a trifunctional or higher functional group. Further, it is preferred to use a plurality of these acrylic resins or methacrylic resins.

Here, the material for forming the organic layer 14 is preferably an ultraviolet curable resin or an electron beam curable resin. By using an ultraviolet curable resin or an electron beam curable resin as a material for forming the organic layer 14, the peeling force with the peeling resin layer 20 can be easily adjusted by the irradiation amount of ultraviolet rays or electron beams, and strong peeling force can be realized. . Therefore, the gas barrier film 10 can be configured to be peeled off at the interface between the peeling resin layer 20 and the substrate 12.

Further, the material for forming the organic layer 14 is a resin material containing 5% or more and less than 50% of an acrylate having one or more functional groups of an adamantane skeleton, or a bismuth or more having a fluorene skeleton of 5% or more and less than 50%. The acrylate resin material is preferred. By using a resin material containing a monofunctional or higher acrylate having an adamantane skeleton or a acrylate having a bifunctional or higher functional group having an anthracene skeleton as a material for forming the organic layer 14, it is possible to maintain a high glass transition temperature Tg. The state reduces the shrinkage ratio at the time of hardening shrinkage, and can prevent the inorganic layer 16 formed on the organic layer 14 from being broken.

The organic layer 14 may be formed (formed into a film) by a known method of forming a layer composed of an organic compound in accordance with the formed organic layer 14. As an example, a coating method can be exemplified.

The organic layer 14 can be formed by preparing a coating composition containing, for example, an organic solvent, an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.) which becomes the organic layer 14, and a crosslinking agent. The coating composition is applied onto the release resin layer 20 to form a coating film, and the coating film is dried and hardened. It is formed by a coating method, whereby a thinner organic layer 14 can be obtained.

In addition, when the gas barrier film 10 has a plurality of organic layers 14, the thickness of each of the organic layers 14 may be the same or different from each other. Further, the material for forming each of the organic layers 14 may be the same or different.

The inorganic layer 16 is a layer composed of an inorganic compound. In the gas barrier film 10, the target gas barrier property is mainly exhibited by the inorganic layer 16.

The material for forming the inorganic layer 16 is not limited, and various layers composed of an inorganic compound exhibiting gas barrier properties can be used. Specifically, a metal oxide such as aluminum oxide, magnesium oxide, cerium oxide, zirconium oxide, titanium oxide or indium tin oxide (ITO); a metal nitride such as aluminum nitride; and a metal carbide such as aluminum carbide can be preferably exemplified. Oxide compounds such as cerium oxide, cerium oxide oxynitride, cerium oxide cerium oxide, cerium oxide oxysulfide, cerium nitride such as tantalum nitride or cerium nitride; cerium carbide such as cerium carbide; hydride thereof; a mixture of the above; and a film composed of an inorganic compound such as a hydrogen-containing substance. Further, a mixture of two or more of them can be used. In particular, the metal oxide and the nitride, specifically, tantalum nitride, cerium oxide, cerium oxynitride, aluminum oxide, or a mixture of two or more thereof, have high transparency and exhibit excellent gas barrier properties. It can be preferably utilized. Among them, in particular, cerium nitride, cerium oxide, and a mixture thereof are further preferably used in addition to excellent gas barrier properties, high transparency, and high flexibility.

Regarding the formation of such an inorganic layer 16, CCP-CVD (capacitive coupling type plasma chemical vapor deposition method) or ICP-CVD (inductively coupled plasma chemical vapor deposition method) is used depending on the formation material of the inorganic layer 16. A known vapor phase film formation method such as sputtering or vacuum deposition may be used.

Regarding the film thickness of the inorganic layer 16, the thickness of the target gas barrier property can be appropriately determined depending on the material to be formed. According to the study by the inventors of the present invention, the thickness of the inorganic layer 16 is preferably from 10 to 200 nm, more preferably from 15 to 100 nm, and particularly preferably from 20 to 75 nm. By setting the thickness of the inorganic layer 16 to 10 nm or more, sufficient gas barrier performance can be stably exhibited. Further, the inorganic layer 16 is usually brittle, and if it is too thick, cracking, cracking, peeling, or the like may occur, and by setting the thickness of the inorganic layer 16 to 200 nm or less, cracking can be prevented.

Further, when the gas barrier film 10 has a plurality of inorganic layers 16, the thickness of each of the inorganic layers 16 may be the same or different. Further, the material for forming each of the inorganic layers 16 may be the same or different.

The gas barrier film 10 has a release resin layer 20 between the substrate 12 and the organic layer 14. As described above, the release resin layer 20 is a resin layer which is adhered to the organic layer 14 and which can be peeled off from the substrate 12 at the interface with the substrate 12. The release resin layer 20 peels off the substrate 12 from the gas barrier layer 18. The release resin layer 20 is a layer that functions as a stress relaxation layer that suppresses application of shear force to the inorganic layer 16 when the substrate 12 is peeled off. Further, after the substrate 12 is peeled off, the release resin layer 20 also functions as a support.

The release resin layer 20 has a low water content and is preferably high in heat resistance. As described above, the inorganic layer 16 exhibiting high gas barrier properties is formed by vacuum film formation such as plasma CVD. When the water content of the release resin layer 20 is high, moisture is released even if vacuum extraction is performed. Therefore, there is a fear that the degree of vacuum cannot be made high and the inorganic layer 16 cannot be formed. In addition, even when the inorganic layer 16 is formed, if the resin layer 20 is stretched and contracted by absorption and release of moisture, the inorganic layer 16 is broken, and high gas barrier properties cannot be obtained. Therefore, the water content of the release resin layer 20 is preferably low. Further, in order to form the inorganic layer 16 by plasma CVD or the like, heat resistance is preferably high.

The glass transition temperature Tg of the cycloolefin copolymer (COC) or the cycloolefin polymer (COP) is a material for forming the release resin layer 20 from the viewpoints of adhesion of the substrate 12 to the organic layer 14, water resistance, heat resistance, and the like. A cyclic olefin resin of 100 ° C or more is preferred.

Further, as described above, the organic layer 14 is formed on the release resin layer 20 by, for example, coating. Thereby, a cycloolefin copolymer (COC) is used as the release resin layer 20 from the viewpoint of the coating property of the coating composition of the organic layer 14 and the optical properties such as solvent resistance and retardation (RETARDATION). It is preferred to form a material.

Such a release resin layer 20 can be formed, for example, by the same coating method as the organic layer 14. It is formed by a coating method, whereby a thin peeling resin layer 20 can be obtained.

The thickness of the release resin layer 20 may be appropriately set depending on the material for forming the release resin layer 20 or the characteristics of the organic layer 14, the inorganic layer 16, and the substrate 12. According to the study by the inventors of the present invention, the thickness of the release resin layer 20 is preferably 0.1 to 25 μm, more preferably 0.5 to 15 μm, and particularly preferably 1 to 10 μm. When the thickness of the peeling resin layer 20 is 0.1 μm or more, the adhesion to the substrate 12 and the organic layer 14 can be appropriately controlled, and the peeling can be easily performed at the interface with the substrate 12, and the substrate 12 can be peeled off. The shear force applied to the inorganic layer 16 is lowered to prevent the inorganic layer 16 from being broken. In addition, when the thickness of the peeling resin layer 20 is 25 μm or less, problems such as cracking of the peeling resin layer 20 and warpage of the gas barrier film 10 due to the excessive thickness of the peeling resin layer 20 can be preferably suppressed. Further, the gas barrier film 10 can be easily wound into a roll shape.

Moreover, from the viewpoint of stress relaxation at the time of peeling off the substrate 12, the hardness of the release resin layer 20 is preferably lower than the hardness of the organic layer 14, and the Young's modulus of the release resin layer 20 is younger than that of the organic layer 14. A low modulus is preferred. That is, it is preferable that the release resin layer 20 is softer than the organic layer 14.

Here, the thickness of the release resin layer 20 is preferably thicker than the thickness of the organic layer 14. As described above, the heat resistance of the organic layer 14 which is the underlayer of the inorganic layer 16 is preferably high. Therefore, it is preferable to use a material having a high glass transition temperature Tg as a material for forming the organic layer 14. Here, in general, a material having a high glass transition temperature Tg is hard and difficult to extend, so that the thickness of the harder organic layer 14 is made thinner, and the thickness of the softer release resin layer 20 is made thicker. The release resin layer 20 can be used as a stress relaxation layer to function reasonably, and high gas barrier properties can be obtained by preventing the inorganic layer 16 from being broken when the substrate 12 is peeled off.

Moreover, the peeling force of the peeling resin layer 20 and the substrate 12, and the peeling force of the peeling resin layer 20 and the organic layer 14 are the peeling force of the peeling resin layer 20 and the organic layer 14 rather than the peeling force of the peeling resin layer 20 and the board|substrate 12. High is not limited. Further, the peeling force of the release resin layer 20 and the substrate 12 is preferably 0.04 N/25 mm to 1 N/25 mm. When the peeling force of the peeling resin layer 20 and the substrate 12 is in the above range, it is possible to suppress the peeling force from being excessively peeled off during transportation, and it is possible to suppress the peeling force from being excessively strong on the substrate 12 . The inorganic layer 16 is damaged during the peeling, and the gas barrier film 10 is deformed. Further, the peeling force (adhesion force) may be measured in accordance with the 180° peeling test method of JIS Z 0237.

The organic protective layer 24 is a layer composed of an organic compound, and is a layer formed on the upper side of the gas barrier layer 18 (more specifically, the inorganic layer 16) and protecting the gas barrier layer 18.

The material for forming the organic protective layer 24 is not particularly limited, and various known organic compounds similar to those of the organic layer 14 can be used.

When the organic protective layer 24 is an adhesive layer, the material for forming it is not limited, and a plurality of well-known adhesive materials can be used. From the viewpoint of optical characteristics, particularly from the viewpoints of retardation and haze, an acrylic adhesive is preferably used as the adhesive material. As the acrylic adhesive, SK DYNE series (manufactured by Soken Chemical & Engineering Co., Ltd.) and the like can be exemplified.

The thickness of the organic protective layer 24 may be appropriately set depending on the material of the organic protective layer 24 or the characteristics of the inorganic layer 16. According to the study by the inventors of the present invention, the thickness of the organic protective layer 24 is preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm, and particularly preferably 1 to 10 μm. The thickness of the organic protective layer 24 is set to 0.1 μm or more, whereby the inorganic layer 16 can be reasonably protected. Moreover, the thickness of the organic protective layer 24 is 50 μm or less, whereby the workability when the gas barrier film 10 is attached to the object to be transferred can be improved.

The protective film 26 can utilize various known sheets which are used as a known protective film. As an example, a film (resin film) composed of various resin materials exemplified in the substrate 12 can be preferably exemplified.

In the case where the protective film 26 is formed on the surface of the gas barrier layer 18 (more specifically, the inorganic layer 16), the Young's modulus of the material for forming the protective film 26 is preferably 6 GPa or less. In this case, the protective film 26 is attached to the inorganic layer 16 of the gas barrier layer 10 which is the uppermost layer of the gas barrier layer 18, and is peeled off from the inorganic layer 16 when the gas barrier film 10 is transferred. . When the Young's modulus of the material for forming the protective film 26 is 6 GPa or less, damage to the inorganic layer 16 generated when the protective film 26 is peeled off can be further preferably prevented, and high gas barrier properties can be obtained. . From this viewpoint, LDPE, HDPE, PP, PET, PEN, PVC, PI, or the like can be preferably exemplified as a material for forming the protective film 26.

The thickness of the protective film 26 may be appropriately set depending on the desired thickness of the gas barrier film 10, the Young's modulus of the material forming the protective film 26, and the like. According to the study by the inventors of the present invention, the thickness of the protective film 26 is preferably 10 to 300 μm, more preferably 30 to 50 μm. By setting the thickness of the protective film 26 to 10 μm or more, it is possible to preferably prevent damage of the inorganic layer 16 caused by an impact or the like received from the outside during winding, and it is possible to suppress wrinkles and deformation generated during transportation. It is preferred in these respects. The thickness of the protective film 26 is set to 300 μm or less, whereby the gas barrier film 10 can be prevented from being excessively thick, which is preferable in this respect.

In the protective film 26, an adhesive layer can be formed on one surface of the inorganic layer 16 side.

Next, a transfer method of the gas barrier film of the present invention (also referred to as "transfer method of the present invention") will be described. In the method for transferring a gas barrier film of the present invention, one surface of the gas barrier film opposite to the substrate is attached to the transfer target, and the substrate is peeled off, thereby providing a gas barrier layer and a release resin layer. The transfer layer is transferred to the transfer target. Hereinafter, the transfer method of the present invention will be described with reference to FIGS. 4(A) to 4(C) and FIG.

4(A) to 4(C) show an example in which a gas barrier film 10b having an organic protective layer 24 as an adhesive layer as shown in FIG. 2(A) is used as a gas barrier film, and This gas barrier film 10b is transferred to the retardation film 112 as a transfer target.

First, as shown in FIG. 4(A) and FIG. 4(B), one surface of the gas barrier film 10b on the opposite side to the substrate 12, that is, the organic protective layer 24 side is bonded to the retardation film 112 side. The bonding method is not limited, and a bonding method of various known film materials can be used. Further, such bonding may be carried out in a sheet type, or a long-sized gas barrier film 10b and a retardation film 112 may be used, and may be bonded by roll-to-roll (hereinafter also referred to as RtoR).

Further, in the illustrated example, the gas barrier film 10b is configured to have an adhesive layer. However, the present invention is not limited thereto, and the adhesive can be applied to the transfer target before being bonded to the gas barrier film 10b. The gas film 10b is attached. Further, when the protective film 26 is provided on the organic protective layer 24 (or the inorganic layer 16), the protective film 26 is peeled off and attached to the transferred body before the gas barrier film is bonded to the transfer target. Just fine.

Next, as shown in FIG. 4(C), the substrate 12 is peeled off from the gas barrier film 10b bonded to the retardation film 112. The method of peeling off the substrate 12 is not limited, and various known methods of peeling off the film can be used. Further, the peeling of the substrate 12 may be performed in a sheet type or by RtoR.

Thereby, the transfer layer 30 of the gas barrier film 10b is transferred to the retardation film 112 as the transfer target, and the retardation film 110 having the gas barrier layer as shown in FIG. 5 can be used. In the transfer method of the gas barrier film of the present invention, the inorganic layer 16 can be prevented from being broken when the substrate 12 is peeled off. Therefore, the transfer layer 30 can be transferred to the transfer target while maintaining high gas barrier properties. Moreover, since the thickness of the transfer layer 30 can be made very thin, it is possible to reduce the influence on optical characteristics such as transparency and retardation value.

Further, in the present invention, the transfer target to which the gas barrier film is transferred is not limited. From the viewpoint of having high gas barrier properties, high transparency, and excellent optical characteristics at low retardation, it can be preferably used for optical members such as organic EL elements and wavelength conversion materials which require high gas barrier properties. Sealed. Moreover, it is used as an optical film and a gas barrier film by providing a high gas barrier property to various optical films.

Hereinafter, members using the gas barrier film of the present invention will be described. The retardation film 110 with a gas barrier layer shown in FIG. 5 which is an example of the retardation film with a gas barrier layer of the present invention, which has a gas barrier film of the present invention, has a transfer layer laminated on the retardation film 112. In the structure of 30, the transfer layer 30 has an organic protective layer 24, an inorganic layer 16, an organic layer 14, and a release resin layer 20. In the retardation film 110 with a gas barrier layer, since the thickness of the transfer layer 30 is extremely thin, it is possible to have a high gas barrier based on the optical characteristics of the retardation film itself in order to suppress the increase in thickness. Film of sex.

Fig. 6 is an example of a wavelength conversion film in which a gas barrier film of the present invention is transferred to seal a wavelength conversion layer. The wavelength conversion film 100 shown in FIG. 6 has a wavelength conversion layer 102, a gas barrier film 104 laminated on one surface of the wavelength conversion layer 102, and a transfer layer 30 laminated on the other surface of the wavelength conversion layer 102.

The wavelength conversion layer 102 has a function of converting and outputting the wavelength of incident light, and is, for example, a quantum dot layer in which quantum dots are dispersed in a binder such as a resin. The type of the quantum dot contained in the quantum dot layer is not particularly limited, and a plurality of well-known quantum dots may be appropriately selected depending on the performance of the desired wavelength conversion or the like. Further, the type of the binder contained in the quantum dot layer is not particularly limited, and a plurality of known binders may be appropriately selected depending on the type of the quantum dot, the desired performance, and the like.

The gas barrier film 104 is used for sealing the wavelength conversion layer 102, and is not particularly limited as long as it has gas barrier properties required for sealing the wavelength conversion layer 102, and a known gas barrier film can be suitably used.

As shown in FIG. 6, the wavelength conversion film 100 seals one surface of the wavelength conversion layer 102 by the conventional gas barrier film 104, and uses the transfer layer 30 transferred from the gas barrier film 10 of the present invention to the other surface. Perform the seal. As described above, at least one surface of the wavelength conversion layer is sealed by the gas barrier film of the present invention, whereby the thickness of the entire wavelength conversion film can be made thin.

Further, in the example shown in FIG. 6, the gas barrier film of the present invention is used to seal one surface of the wavelength conversion layer. However, the present invention is not limited thereto, and the gas barrier film pair of the present invention may be used. The structure in which the two surfaces of the wavelength conversion layer are sealed. Thereby, the thickness of the entire wavelength conversion film can be made thinner.

7(A) to 7(C) are examples of the organic EL laminate in which the organic EL element is sealed by transferring the gas barrier film of the present invention.

The organic EL laminate 120a shown in FIG. 7A has an element substrate 122, an organic EL element 124 formed on the element substrate 122, and a transfer layer 30 laminated with the organic EL element 124. The element substrate 122 can utilize all of the element substrates for various organic EL devices. Specifically, an element substrate made of glass, plastic, metal, ceramics or the like can be exemplified. Moreover, in order to prevent deterioration of the organic EL element 124 due to moisture or the like, it is preferable to prevent the water from penetrating the element substrate 122 and to reach the organic EL element 124. Therefore, as the element substrate 122, a substrate made of a material such as glass or metal, which has a low content of moisture or the like and a low transmittance of moisture or the like is preferably used.

Further, as the organic EL laminate 120b shown in Fig. 7(B), the gas barrier film 10 (more specifically, the transfer layer 30) of the present invention can be used as the element substrate. Alternatively, a person who transfers the gas barrier film 10 of the present invention to a resin substrate can be used as the element substrate.

The organic EL element 124 is, for example, a known organic EL element having an organic electroluminescence layer, a transparent electrode and a reflection electrode as an electrode pair sandwiching the organic electroluminescence layer. As shown in the figure, the organic EL element 124 is sealed by the transfer layer 30 transferred by the gas barrier film 10 of the present invention. By sealing the organic EL element 124 by the gas barrier film of the present invention, the thickness of the entire organic EL laminate can be made thin.

Further, the organic EL laminate may be a top emission type that emits light from the transfer layer 30 side, or may be a bottom emission type that emits light from the element substrate 122 side.

Further, as the organic EL laminate 120c shown in FIG. 7(C), a passivation film 126 may be provided between the organic EL element 124 and the transfer layer 30. That is, the organic EL element 124 can be sealed by the passivation film 126, and the structure of the transfer layer 30 can be transferred onto the passivation film 126. The passivation film 126 is for preventing moisture, oxygen, and the like from reaching the organic EL element 124 and degrading the organic EL element 124. It can be used for a known organic EL device, and various films (layers) composed of a material exhibiting gas barrier properties can be used as such a passivation film 126. Specifically, a film having gas barrier properties similar to the inorganic layer 16 and composed of an inorganic compound such as tantalum nitride or ruthenium oxide can be exemplified. The passivation film 126 may be formed by a known method depending on the material for forming the film.

Hereinafter, a method for producing a gas barrier film of the present invention will be described with reference to Figs. 8(A) and 8(B). Further, in the following examples, it is preferable to use the long-length substrate 12, the protective film 26, and the like, and to manufacture a gas barrier film by RtoR. As is well known, RtoR refers to a process in which a material to be processed is wound from a roll obtained by winding a long-sized object to be processed, and is conveyed in the longitudinal direction while film formation is performed, and the processed object to be processed is again wound into a roll. Manufacturing method.

First, the release resin layer 20 is formed on the substrate 12 by using the film forming apparatus schematically shown in FIG. 8(A). Specifically, for example, a coating composition containing an organic solvent and an organic compound which becomes the release resin layer 20 is prepared. On the other hand, the substrate roll Ra is loaded at a predetermined position of the organic film forming apparatus, and the substrate roll Ra is formed by winding the long-sized substrate 12 into a roll shape. Next, the substrate 12 is fed out from the substrate roll Ra to pass the paper in a predetermined path to the winding position. Further, the coating composition to be the release resin layer 20 is filled in a predetermined position of the coating portion 40. The film forming apparatus has a transport roller pair 48 for transporting the substrate 12 along a predetermined path. Then, the substrate 12 is sent out from the substrate roll Ra and transported in the longitudinal direction, and the prepared coating composition is applied to the substrate 12 in the coating portion 40, and then the applied coating composition is applied to the drying portion 42. Drying is carried out, and ultraviolet light irradiation or heating or the like is performed on the hardened portion 44 as necessary to form the release resin layer 20. Moreover, the long-length film in which the peeling resin layer 20 was formed on the board|substrate 12 was wound in the roll shape as the base material roll Rb. Moreover, although illustration is abbreviate|omitted, it is preferable to laminate|stack the protective film after formation of the peeling resin layer 20, and it is winding up as the base material roll Rb.

Next, the substrate 12 on which the release resin layer 20 is formed is used as the film formation substrate Za, and the organic layer 14 is formed on the release resin layer 20 of the film formation substrate Za. The formation of the organic layer 14 may be carried out in substantially the same manner as the method of forming the release resin layer 20 using the organic film forming apparatus shown in FIG. 8(A). That is, a coating composition containing, for example, an organic solvent, an organic compound which becomes the organic layer 14, and a polymerization initiator is prepared. Further, the substrate roll Rb is loaded at a predetermined position of the organic film forming apparatus, and the base roll Rb is formed by winding a long film-formed substrate Za into a roll shape. Next, the film formation substrate Za is sent out from the substrate roll Rb, and the paper is passed through a predetermined path to the winding position. Further, the coating composition to be the organic layer 14 is filled in a predetermined position of the coating portion 40. Then, the coated substrate 30 is fed from the substrate roll Rb and transported in the longitudinal direction, and the prepared coating composition is applied onto the release resin layer 20 in the coating unit 40, followed by the drying unit 42. The applied coating composition is dried, and the organic layer 14 is formed by polymerizing (crosslinking) the organic compound in the hardened portion 44 by ultraviolet irradiation or the like. Moreover, the long dimension of the organic layer 14 is formed by winding the film formation substrate Za into a roll shape as the substrate roll Rc.

In addition, the protective film may be attached to the organic layer 14 after the organic layer 14 is formed. The attachment of the protective film is preferably performed before the organic layer 14 comes into contact with other members such as the guide rolls. Thereby, the organic layer 14 which is the underlying layer of the inorganic layer 16 can be prevented from being damaged, and the inorganic layer 16 can be formed reasonably on the smooth organic layer 14, so that a gas barrier film which exhibits high gas barrier properties can be obtained. Moreover, in the above-described example, the film formation of the peeling resin layer 20 and the film formation of the organic layer 14 are respectively performed. However, the present invention is not limited thereto, and after the film formation of the release resin layer, the film may be unwound. The film formation of the organic layer 14 is continued in the state. In other words, the film formation apparatus can continuously perform the film formation of the release resin layer 20 and the film formation of the organic layer 14, and the film formation apparatus can arrange the coating portion 40 for forming the release resin layer 20 in the conveyance path of the substrate 12. The drying unit 42 and the curing unit 44, and the coating unit 40, the drying unit 42, and the curing unit 44 for forming the organic layer 14.

Next, in the inorganic film forming apparatus generally shown in FIG. 8(B), the substrate 12 on which the release resin layer 20 and the organic layer 14 are formed (hereinafter, sometimes referred to as "film formation substrate Zb") is used. The inorganic layer 16 is formed, and the protective film 26 is attached to the inorganic layer 16 to form the gas barrier film 10. The inorganic film forming apparatus shown in FIG. 8(B) is an example in which the inorganic layer 16 is formed by CCP-CVD (capacitive coupling type plasma chemical vapor deposition method), and has a supply chamber 50 and a film forming chamber 52. And the take-up chamber 54. First, the substrate roll Rc is loaded into a predetermined position of the supply chamber 50. Next, the film formation substrate Zb is sent out from the substrate roll Rc, and the paper passes through a predetermined path from the supply chamber 50 to the winding chamber 54 through the film forming chamber 52. The substrate roll Rc is loaded so that the organic layer 14 becomes a film formation surface in the film formation chamber 52. Further, the protective film roll 26R is loaded at a predetermined position of the film forming chamber 52. Next, the protective film 26 is sent out from the protective film roll 26R, and the paper passes through a predetermined path from the film forming chamber 52 to the winding chamber 54.

Next, the supply chamber 50 is evacuated to the film forming chamber 52 by the vacuum exhausting means 52a, and the winding chamber 54 is exhausted by the vacuum exhausting means 54a to evacuate the respective chambers. Until it becomes the prescribed pressure. After the respective chambers have reached a predetermined pressure, the film formation substrate Zb and the protective film 26 are started to be conveyed.

The film formation substrate Zb is sent out from the substrate roll Rc and guided to the guide roller 58, thereby being conveyed to the film formation chamber 52. The film formation substrate Zb conveyed to the film formation chamber 52 is guided to the guide roller 60 and wound around the circumferential surface of the cylindrical drum 62. The roller 62 also functions as an electrode in CCP-CVD. Further, as a preferred embodiment, the drum 62 has a temperature adjustment function. The film formation substrate Zb is formed as a laminated film in which the inorganic layer 16 is formed by CCP-CVD while being conveyed along a predetermined path by the roller 62, and the release resin layer 20 and the organic layer are formed on the substrate 12. The combination of layer 14 and inorganic layer 16. The CCP-CVD system has a film forming means such as an electrode pair composed of a drum 62 and a shower electrode 64, a material gas supply unit 68, and a high-frequency power source 70. The formation of the inorganic layer 16 by plasma CVD may be carried out by a known method in accordance with the formation material of the inorganic layer 16 or the like. Further, in addition to CCP-CVD, various known vapor phase film formation methods such as ICP-CVD (inductively coupled plasma chemical vapor deposition), sputtering, and vacuum deposition can be used for the formation of the inorganic layer 16.

On the other hand, in synchronization with the conveyance of the film formation substrate Zb, the protective film 26 is sent out from the protective film roll 26R and conveyed in the longitudinal direction. The film-forming substrate Zb on which the inorganic layer 16 is formed and the protective film 26 are laminated and laminated by the laminating roller pair 72, whereby the gas barrier film 10 is produced. Further, an adhesive layer may be formed on the surface opposite to the inorganic layer 16 of the protective film 26.

When the gas barrier film 10 is produced by RtoR, it is preferable that the protective film 26 is attached after the inorganic layer 16 is formed, and before the inorganic layer 16 is brought into contact with other members such as a guide roll. Thereby, the inorganic layer 16 is prevented from being damaged, and the gas barrier film 10 exhibiting the target gas barrier property can be obtained.

The gas barrier film 10 produced by laminating and attaching the laminated film of the laminated roller pair 72 and the protective film 26 is conveyed from the film forming chamber 52 to the winding chamber 54, and guided by the guide roller 76 along a predetermined path. The film is taken up to form a barrier film roll Rd for winding the long-size gas barrier film 10.

In addition, when the film formation substrate Zb is a protective film on the organic layer 14, the inorganic layer 16 may be formed after the protective film is peeled off before the inorganic layer 16 is formed. The peeling of the protective film is preferably carried out at a position of a film forming means that reaches the inorganic layer 16, that is, at a position where a member such as a guide roll that is in contact with the organic layer 14 is not present.

Further, when the organic protective layer 24 is further formed on the inorganic layer 16, the substrate 12 on which the release resin layer 20, the organic layer 14 and the inorganic layer 16 are formed is used as a film formation substrate, and as shown in Fig. 8(A) The organic film forming apparatus shown may be formed in the same manner as the peeling resin layer 20 and the organic layer 14.

The gas barrier film of the present invention has been described in detail above, but the present invention is not limited to the above-described embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention. [Examples]

Hereinafter, the present invention will be described in further detail with reference to specific embodiments of the invention.

[Example 1] As the first example, the gas barrier film 10a shown in Fig. 1(A) was produced.

<Formation of Release Resin Layer 20> A long-length PET film (Cosmo shine A4100, manufactured by TOYOBO CO., LTD.) having a width of 1000 mm, a thickness of 50 μm, and a length of 100 m was used as the substrate 12. The release resin layer 20 is formed on the unprimed surface side of the substrate 12 in the following procedure.

The COC resin (APEL 6015T manufactured by Mitsui Chemicals, Inc.) was dissolved in cyclohexane to prepare a coating liquid having a solid concentration of 10% as the coating liquid A1 to be the release resin layer 20. This coating liquid A1 is filled in the coating portion 40 of the film forming apparatus according to RtoR as shown in Fig. 8(A). The coating unit 40 uses a die coater. Moreover, the substrate roll Ra in which the substrate 12 is wound into a roll is loaded at a predetermined position, and the substrate 12 is inserted through the predetermined transport path. In addition, the coating liquid A1 is applied onto the substrate 12 by the coating portion 40 so that the dried film thickness is 2 μm while the substrate 12 is conveyed in the longitudinal direction, and dried at a drying temperature of 100 ° C in the drying portion 42. The peeling resin layer 20 was formed on the substrate 12 by 3 minutes. The hardened portion 44 is not used at this time. That is, the material forming the release resin layer 20 is a cyclic olefin copolymer.

The glass transition temperature Tg of the formed release resin layer 20 was measured by a high-sensitivity differential scanning calorimeter (manufactured by Hitachi High-Tech Science Corporation, DSC7000X) in accordance with JIS K 7121, and the result was 145 °C.

<Formation of Organic Layer 14> Next, the organic layer 14 is formed on the formed release resin layer 20 in the following procedure. A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) were prepared and weighed in such a manner that the weight ratio became 97:3, and they were dissolved in methyl group. A coating liquid having a solid concentration of 15% was prepared as ethyl ketone to obtain a coating liquid B1 as the organic layer 14.

This coating liquid B1 is filled in the coating portion 40 of the film forming apparatus according to RtoR as shown in Fig. 8(A). The coating unit 40 uses a die coater. In addition, the substrate roll Rb obtained by winding the substrate 12 having the peeling resin layer 20 (hereinafter sometimes referred to as "film formation substrate Za") into a roll shape is loaded at a predetermined position and inserted through a predetermined transport path. Film-forming substrate Za. In addition, the coating liquid B1 is applied onto the release resin layer 20 of the film formation substrate Za by the coating portion 40 so that the film thickness of the film formation substrate is in the longitudinal direction and the dry film thickness is 1 μm. And drying in the drying section 42 at a drying temperature of 50 ° C for 3 minutes, and curing the hardened portion 44 with ultraviolet rays (accumulated irradiation amount of about 700 mJ/cm ² ), thereby forming an organic layer on the release resin layer 20. 14. Further, after the organic layer 14 is hardened and before the contact with the roll which is initially in contact with the surface on the organic layer 14 side, a polyethylene protective film is attached to the organic layer 14, and then wound up.

The glass transition temperature Tg of the formed organic layer 14 was measured by a high-sensitivity differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., DSC7000X) in accordance with JIS K 7121, and the result was measured at 250 ° C or higher. Upper limit.

<Formation of Inorganic Layer 16> Next, the inorganic layer 16 is formed on the formed organic layer 14 in the following procedure. The substrate roll Rc obtained by winding the substrate 12 on which the release resin layer 20 and the organic layer 14 are formed (hereinafter sometimes referred to as "film formation substrate Zb") into a roll shape is loaded as shown in FIG. 8(B). A predetermined position of the supply chamber 50 of the film forming apparatus is shown, and the protective film roll 26R is loaded at a predetermined position of the film forming chamber 52. Further, the film formation substrate Zb is sent out from the substrate roll Rc, and the paper is conveyed in a predetermined conveyance path from the supply chamber 50 to the winding chamber 54 through the film formation chamber 52. Moreover, the protective film 26 is sent out from the protective film roll 26R, and the paper is conveyed along the predetermined conveyance path from the film forming chamber 52 to the winding chamber 54. In this state, the film-forming substrate Zb and the protective film 26 are simultaneously conveyed, and the protective film is peeled off from the film-formed substrate Zb after the film surface before the film formation is brought into contact with the roll, and is supported/guided to A surface of the organic layer 14 of the film formation substrate Zb of the roll 62 in the film formation chamber 52 is formed as a inorganic layer 16 by CCP-CVD. Next, the gas barrier film 10a shown in FIG. 1 is formed by laminating and laminating the protective film 26 on the inorganic layer 16 by the laminating roller pair 72, and winding up.

In the formation of the inorganic layer 16, a decane gas (flow rate: 160 sccm), ammonia gas (flow rate: 370 sccm), and hydrogen gas (flow rate: 2000 sccm) were used as a material gas. The power supply uses a high frequency power supply having a frequency of 13.56 MHz, and the plasma excitation power is set to 8 kW. The film formation pressure was set to 40 Pa. The film thickness of the inorganic layer 16 was 30 nm. The attachment of the protective film 26 is performed after the inorganic layer 16 is formed and before the inorganic layer 16 is brought into contact with other members. Further, a polyethylene film is used as the protective film 26.

[Example 2] A gas barrier film 10b as shown in Fig. 2(A) was produced in the same manner as in Example 1 except that the organic protective layer 24 shown below was formed on the inorganic layer 16. .

Polyurethane skeleton acrylic polymer (ACRIT 8BR930 manufactured by TAISEI FINE CHEMICAL CO., LTD.), photopolymerization initiator (Irg 184 manufactured by BASF JAPAN LTD.), decane coupling in a weight ratio of 78:10:10:2 A solution (KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and a softener (BYRON U1400 manufactured by TOYOBO CO., LTD.) were weighed and dissolved in methyl ethyl ketone to prepare a solid concentration of 15%. The coating liquid serves as the coating liquid C1 which becomes the organic protective layer 24. This coating liquid C1 is filled in the coating portion 40 of the film forming apparatus according to RtoR as shown in Fig. 8(A). The coating unit 40 uses a die coater. Further, the substrate 12 on which the peeling resin layer 20, the organic layer 14 and the inorganic layer 16 are formed (hereinafter sometimes referred to as "film formation substrate Zc") is wound into a roll, and the substrate roll is loaded in a predetermined position. The film formation substrate Zc is inserted through the predetermined conveyance path. In addition, the coating liquid C1 is applied onto the inorganic layer 16 of the film formation substrate Zc by the coating portion 40 so that the film thickness of the film formation substrate Zc is increased in the longitudinal direction, and the dry film thickness is 1 μm. The drying portion 42 is dried at a drying temperature of 100 ° C for 3 minutes, and is cured by irradiating ultraviolet rays (accumulated irradiation amount of about 600 mJ/cm ² ) to the hardened portion 44, whereby an organic protective layer 24 is formed on the inorganic layer 16. .

[Example 3] The following coating liquid C2 was used as the coating liquid to be the organic protective layer 24, and the thickness of the organic protective layer 24 was set to 3 μm, and after the machine protective layer 24 was formed, by the same manner as described above In the same manner as in Example 2, as shown in Fig. 2(B), the first film surface contact roller was attached with a separator (FILM BYNA BD manufactured by FUJIMORI KOGYO CO., LTD.) as the protective film 26. Gas barrier film 10c. With respect to the coating liquid C2, hardened 剤L-45 (manufactured by Soken Chemical & Engineering Co., Ltd.) was added to SK DYNE NT21 (manufactured by Soken Chemical & Engineering Co., Ltd.) at a ratio of 100:2, and Dilute to butyl acetate to prepare a solid concentration of 15%. The organic protective layer 24 is an acrylic adhesive.

[Example 4] A gas barrier was produced in the same manner as in Example 3 except that a polyurethane-based adhesive (No. 96 manufactured by ROCK PAINT CO., LTD.) was used as the coating liquid C3 to be the organic protective layer 24. Film 10c. The organic protective layer 24 is a polyurethane-based adhesive.

[Example 5] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid A2 was used as the coating liquid to be the release resin layer 20. With respect to the coating liquid A2, COC resin (APEL 6509T manufactured by Mitsui Chemicals, Inc.) was dissolved in cyclohexane, and the solid content concentration was 10%. The glass transition temperature Tg of the formed release resin layer 20 was measured in the same manner as above, and was 70 °C.

[Example 6] A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid A3 was used as the coating liquid to be the release resin layer 20. With respect to the coating liquid A3, COC resin (APEL 6011T manufactured by Mitsui Chemicals, Inc.) was dissolved in cyclohexane, and the solid content concentration was 10%. The glass transition temperature Tg of the formed release resin layer 20 was measured in the same manner as above, and was 105 °C.

[Example 7] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid A4 was used as the coating liquid to be the release resin layer 20. In the coating liquid A4, COP resin (ARTON D4540 manufactured by JSR Corporation) was dissolved in cyclohexane, and the solid content concentration was 10%. The glass transition temperature Tg of the formed release resin layer 20 was measured in the same manner as above, and was 128 °C.

[Example 8] A gas barrier film was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to a dry film thickness of 20 μm. 10a.

[Example 9] A gas barrier film was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to a dry film thickness of 10 μm. 10a.

[Example 10] A gas barrier was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed, and the dry film thickness was 0.5 μm. Film 10a.

[Example 11] A gas barrier was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid A1 to be the release resin layer 20 were changed to a dry film thickness of 0.1 μm. Film 10a.

[Example 12] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid B2 was used as the coating liquid to be the organic layer 14. With respect to the coating liquid B2, A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and A-600 (Tg-22 ° C manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed in a 4:1 manner. The photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) was weighed and dissolved in methyl ethyl ketone at a weight ratio of 97:3 to prepare a solid concentration of 15%. The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as above, and was 180 °C.

[Example 13] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid B3 was used as the coating liquid to be the organic layer 14. With respect to the coating liquid B3, A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and A-600 (Tg-22 ° C manufactured by Shin-Nakamura Chemical Co., Ltd.) were mixed in a ratio of 1:1. The photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) was weighed and dissolved in methyl ethyl ketone at a weight ratio of 97:3 to prepare a solid concentration of 15%. The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as above, and was 114 °C.

[Example 14] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid B4 was used as the coating liquid to be the organic layer 14. EB3702 (Tg53 ° C) and photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) manufactured by DAICEL-ALLNEX LTD. were weighed and dissolved in a coating liquid B4 at a weight ratio of 97:3. The ethyl ketone was prepared to have a solid concentration of 15%. The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as above, and was 53 °C.

[Example 15] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid B5 was used as the coating liquid to be the organic layer 14. With respect to the coating liquid B5, A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-ADMA (1-adamantyl methacrylate OSAKA ORGANIC CHEMICAL INDUSTRY LTD) were mixed in a ratio of 1:1. Tg 250 ° C), and a photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) was weighed and dissolved in methyl ethyl ketone at a weight ratio of 97:3 to prepare a solid concentration of 15%. . That is, the material for forming the organic layer contains one or more functional acrylates having an adamantane skeleton. The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as above, and was 250 °C.

[Example 16] A gas barrier film 10a was produced in the same manner as in Example 1 except that the coating liquid B6 was used as the coating liquid to be the organic layer 14. With respect to the coating liquid B6, A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and EA-200 (Tg211 manufactured by acrylate monomer Osaka Gas Chemicals Co., Ltd.) were mixed in a ratio of 1:1. °C), a photopolymerization initiator (Irg 819 manufactured by BASF JAPAN LTD.) was weighed and dissolved in methyl ethyl ketone at a weight ratio of 97:3 to prepare a solid concentration of 15%. That is, the material for forming the organic layer contains a bifunctional or higher acrylate having an anthracene skeleton. The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as above, and was 230 °C.

[Example 17] A gas barrier film 10a was produced in the same manner as in Example 1 except that an aluminum oxide film (aluminum oxide film) was formed as the inorganic layer 16. The aluminum oxide film is formed by a usual sputtering apparatus. Specifically, an alumina sintered body was used as a target and an inorganic layer 16 composed of an aluminum oxide film was formed by DC magnetron sputtering.

[Example 18] A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid B1 to be the organic layer 14 were changed to a dry film thickness of 5 μm. .

[Example 19] A gas barrier film was produced in the same manner as in Example 1 except that the solid content concentration and the coating amount of the coating liquid B1 to be the organic layer 14 were changed to a dry film thickness of 0.1 μm. 10a.

[Example 20] A gas barrier film 10a was produced in the same manner as in Example 1 except that an oxime release film (FILM BYNA BD manufactured by FUJIMORI KOGYO CO., LTD.) was used as the substrate 12.

[Example 21] A gas barrier film was produced in the same manner as in Example 3 except that the solid content concentration and the coating amount of the coating liquid C2 to be the organic protective layer 24 were changed to a dry film thickness of 50 μm. 10c.

[Example 22] A gas barrier was produced in the same manner as in Example 3 except that the solid content concentration and the coating amount of the coating liquid C2 to be the organic protective layer 24 were changed to a dry film thickness of 0.1 μm. Film 10c.

[Comparative Example 1] A gas barrier film was produced in the same manner as in Example 1 except that the release resin layer 20 was not formed.

[Comparative Example 2] When the release resin layer 20 was formed, after drying, ultraviolet rays having an accumulated irradiation amount of about 3000 mJ/cm ^{2 were} irradiated and cured to be wound up. Next, the cumulative irradiation amount of the ultraviolet rays when the organic layer 14 was formed was changed to about 50 mJ/cm ² . A gas barrier film was produced in the same manner as in Example 1 except the above. Thereby, the peeling force of the peeling resin layer 20 and the substrate 12 is strengthened, and the peeling force of the organic layer 14 and the peeling resin layer 20 is weakened. Thereby, the peeling force of the organic layer 14 and the peeling resin layer 20 is made weaker than the peeling force of the peeling resin layer 20 and the board|substrate 12. That is, it is considered that peeling can be performed between the peeling resin layer 20 and the organic layer 14.

[Evaluation] The gas barrier films of Examples 1 to 22 and Comparative Examples 1 and 2 which were produced were evaluated for gas barrier properties and optical properties.

<Gas-Containing Property> (Transfer Process) A 200 mm square TAC film with an adhesive layer of FUJITAC (manufactured by TD80 Fujifilm Corporation) was attached as an object to be transferred, and an optical adhesive film (manufactured by PDS1 PANAC Corporation) was attached. After the protective film 26 of the gas barrier film 10 thus produced is peeled off, it is bonded by a laminator (Proteus manufactured by Fellowes Japan KK) so that the adhesive layer of the transfer target body and the inorganic layer 16 of the gas barrier film 10 are bonded. Pick up. Thereby, a bonded film of 200 mm square was obtained. The lamination pressure was set to 0.5 MPa, and the conveyance speed was set to 5 m/min. After bonding, the substrate 12 of the gas barrier film 10 is peeled off. The substrate 12 was peeled off as follows. First, a 200 mm square laminated film was punched into a 100 mm square using a Thomson blade so that the end faces were reliably peeled off. Next, the TAC film side is directed downward, and the surface of the TAC film is adsorbed and held by the flat plate having a high planarity, and then about 2 cm of the adhesive tape for gripping the substrate 12 (NITTO SELLO TAPE (registered trademark)) is attached to the end portion. . Next, the bonding tape was pulled apart from the sample in such a manner that the substrate 12 was drawn in the same manner as the 180-degree peeling test. Thus, the substrate 12 is peeled off. At the time of peeling, it was carried out in an environment of a temperature of 25 ° C and a humidity of 50% RH. In addition, in the third embodiment, the fourth embodiment, the twenty-first embodiment, and the twenty-second embodiment, the organic protective layer 24 having the adhesive layer on the inorganic layer 16 is a FUJITAC (manufactured by TD80 Fujifilm Corporation) which is not bonded with a bonded film. Transfer was carried out in the same manner except for the transfer body.

(Water vapor transmission rate measurement) The water vapor of the gas barrier film 10 which is transferred to the object to be transferred and which is peeled off from the substrate 12 by a calcium etching method (method described in JP-A-2005-283561) The transmittance is measured. Regarding the constant temperature and humidity treatment conditions, the temperature was set to 40 ° C and the relative humidity was set to 90% RH. Further, the water vapor transmission rate of the FUJITAC monomer was 400 [g/(m ² day)]. Based on the measured water vapor transmission rate, it was evaluated based on the following criteria. A: water vapor transmission rate is less than 5 × 10 ^-5 [g / (m ² · day)] B: water vapor transmission rate is 5 × 10 ^-5 or more, and less than 1 × 10 ^-4 [g / (m ² • Day)] C: water vapor transmission rate is 1 × 10 ^-4 or more, and less than 5 × 10 ^-4 [g / (m ² · day)] D: water vapor transmission rate is 5 × 10 ^-4 or more, and is smaller than 1 × 10 ^-3 [g / (m ² · day)] E: water vapor transmission rate is 1 × 10 ^-3 [g / (m ² · day)] or more

<Optical Characteristics> After the protective film 26 of the gas barrier film 10 thus produced is peeled off, the substrate 12 is peeled off to take out the transfer layer 30 including the release resin layer 20 and the gas barrier layer 18 (the organic layer 14 and the inorganic layer 16). . Next, the total light transmittance and retardation value of the transfer layer 30 were measured. (Total Light Transmittance) The total light transmittance of the extracted transfer layer 30 was measured by a spectrophotometer (haze meter SH7000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD). The total light transmittance measured was evaluated based on the following criteria. A: Total light transmittance is 90% or more B: Total light transmittance is 88% or more and less than 90% C: Total light transmittance is 86% or more and less than 88% D: Total light transmittance is 84% or more And less than 86%

(delay value) The retardation value (Re値) of the extracted transfer layer 30 was measured by KOBRA-WR (manufactured by Oji Scientific Instruments). The evaluation was based on the measured delay values and based on the following criteria. A: retardation value is 5 nm or less B: retardation value is more than 5 nm and is 10 nm or less C: retardation value is more than 10 nm, and 2 is 0 nm or less D: retardation value is more than 20 nm The results are shown in the following table.

【Table 1】

As shown in the above Table 1, in the embodiment of the present invention in which the peeling resin layer is provided between the substrate and the gas barrier layer and the interface between the peeling resin layer and the substrate is peeled off, the result of comparison with the comparative example shows that the gas barrier is obtained. Excellent in properties and optical properties. Moreover, from the comparison of Example 1, Example 5, and Example 6, it is understood that the cyclic olefin resin having a peeling resin layer-based glass transition temperature Tg of 100 ° C or more is preferable. Further, from the comparison between Example 1 and Example 7, it is understood that the release resin layer is preferably a cycloolefin copolymer. Further, from the comparison between Example 1 and Examples 8 to 11, it is understood that the thickness of the release resin layer is preferably 0.1 to 25 μm, more preferably 0.5 to 15 μm.

Further, from the comparison of Example 1 and Example 12 to Example 14, it is understood that the glass transition temperature Tg of the organic layer is preferably 200 ° C or higher. Further, from the comparison of Example 1, Example 15, and Example 16, it is understood that the organic layer contains 5% or more and less than 50% of an acrylate having one or more functional groups having an adamantane skeleton, or more preferably 5% or more. Preferably, less than 50% of the acrylate having 2 or more functional groups having an anthracene skeleton is preferred. Further, from the comparison of Example 1, Example 18 and Example 19, the thickness of the organic layer is preferably 0.1 to 50 μm, more preferably 0.1 to 5 μm, still more preferably 0.2 to 3 μm. Further, from the comparison between Example 1 and Example 17, it is understood that the inorganic layer is preferably tantalum nitride.

Further, from Examples 2 to 4, Example 21, and Example 22, it is preferable to have the organic protective layer 24 on the inorganic layer 16. Further, from the comparison between Example 3 and Example 4, it is preferable to use an acrylic pressure-sensitive adhesive as the organic protective layer 24. Further, from the comparison of Example 3, Example 21, and Example 22, the thickness of the organic protective layer 24 is preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm.

[Example 23] A wavelength conversion film 100 as shown in Fig. 6 was produced using the gas barrier film 10 produced. The wavelength conversion film is a quantum dot film having a quantum dot layer as a wavelength conversion layer.

<Preparation of Composition for Forming Quantum Dot Layer> The following quantum dot-containing polymerizable composition A was prepared, filtered through a polypropylene film having a pore size of 0.2 μm, and then dried under reduced pressure for 30 minutes to be used as a coating composition. The concentration of quantum dots in the following toluene dispersion was 1% by mass. (content-based polymerizable composition A) Toluene dispersion of quantum dot 1 (luminescence maximum: 520 nm) Toluene dispersion of 10.0 mass fraction of quantum dot 2 (luminescence maximum: 630 nm) 1.0 mass fraction / dodecyl group Acrylate 80.8 parts by mass and trimethylolpropane triacrylate 18.2 part by mass and photopolymerization initiator 1.0 part by mass (IRGACURE 819 (manufactured by BASF Corporation))

<Preparation of Quantum Dot Film> The gas barrier film 10a of Example 1 was prepared as two films (a first film and a second film). That is, the same structure is used as the first film and the second film. First, the protective film 26 on the inorganic layer 16 is peeled off while continuously conveying the first film at a tension of 1 m/min and 60 N/m, and the coating prepared in the above manner is applied onto the inorganic layer 16 by a die coater. The composition was used to form a coating film having a thickness of 50 μm. Next, the film on which the coating film was formed was wound around a support roll. The protective film 26 is peeled off from the second film, and laminated in the direction in which the surface of the inorganic layer 16 is in contact with the coating film. Thus, the coating film is sandwiched between the first film and the second film. In the state of continuous conveyance in this state, the air-cooled metal halide lamp (manufactured by EYE GRAPHICS CO., LTD.) of 160 W/cm was cured by ultraviolet rays after being passed through a heating zone of 60 ° C for 3 minutes. A quantum dot layer (wavelength conversion layer 102) of a sub-point. Further, the irradiation amount of ultraviolet rays was 2000 mJ/cm ² . A quantum dot film (wavelength conversion film 100) was produced by peeling off the substrate 12 from the first film and the second film, respectively.

[Evaluation] The durability of the wavelength conversion film 100 of Example 23 produced was evaluated.

Specifically, the luminance of the wavelength conversion film 100 immediately after the fabrication and the luminance at a temperature of 60 ° C and a humidity of 90% RH are measured for 1000 hours (after humidification), and the amount of change is durable. Sexual evaluation. The luminance was measured as follows. First, a commercially available liquid crystal display device (Kindle Fire HDX7 manufactured by Amazon Inc.) is decomposed, and a backlight unit having a blue light source is taken out. Next, a wavelength conversion film cut into a rectangular shape is placed on the light guide plate of the backlight unit, on which The two prism sheets taken out from the liquid crystal display device are stacked and disposed so as to be orthogonal to the direction of the concave-convex pattern on the surface. The backlight unit is turned on and the luminance is set at a position 740 mm in the vertical direction from the front surface of the backlight unit. The luminance was measured by SR (manufactured by TOPCON CORPORATION).

As a result of the measurement, the change in luminance before and after humidification was 1% or less. Therefore, it is understood that the wavelength conversion film sealed by the gas barrier film of the present invention has high durability.

[Example 24] Using the produced gas barrier film 10, a retardation film 110 with a gas barrier layer as shown in Fig. 5 was produced. A special polycarbonate F138 (manufactured by TEIJIN LIMITED) was used as the retardation film 112. First, an optical bonding film (manufactured by PDS1 PANAC Corporation) was bonded to the retardation film 112. After the protective film 26 of the gas barrier film 10a of the first embodiment is peeled off, it is bonded by a laminator (Proteus manufactured by Fellowes Japan KK) so that the adhesive layer side of the retardation film 112 and the gas barrier film 10 are adhered. The inorganic layers 16 are joined. After bonding, the substrate 12 of the gas barrier film 10 is peeled off to form a retardation film 110 having a gas barrier layer.

[Evaluation] The optical characteristics of the retardation film 110 with a gas barrier layer of Example 24 produced were evaluated.

Specifically, the difference between the retardation values of the retardation film 112 alone and the retardation film 110 having the gas barrier layer was 2% or less. Therefore, it is understood that the retardation film 110 with the gas barrier layer for transferring the gas barrier film of the present invention has high gas barrier properties while maintaining optical characteristics.

[Example 25] An organic EL laminate 120a as shown in Fig. 7(A) was produced using the gas barrier film 10 produced.

<Preparation of Organic EL Element> A glass plate having a thickness of 500 μm and a size of 20 × 20 mm was prepared as the element substrate 122. The periphery of the element substrate 122 was masked by ceramic by 2 mm. Further, the masked element substrate was loaded in a usual vacuum deposition apparatus, and an electrode made of metal aluminum having a thickness of 100 nm was formed by vacuum deposition, and a lithium fluoride layer having a thickness of 1 nm was formed. Next, on the element substrate 122, the following organic compound layers were sequentially formed by vacuum deposition.・(Light-emitting layer and electron transport layer) Tris(8-hydroxyquinoline) aluminum: Film thickness: 60 nm ・(Second hole transport layer) N,N'-diphenyl-N,N'-dinaphthylbenzidine Film thickness: 40 nm ・(first hole transport layer) copper phthalocyanine: film thickness: 10 nm Further, the element substrate 122 on which these layers are formed is loaded in a normal sputtering apparatus and ITO (Indium Tin Oxide Indium Tin Oxide) As a target, a transparent electrode composed of an ITO thin film having a thickness of 0.2 μm was formed by DC magnetron sputtering. In this manner, the organic EL element 124 as a light-emitting element using an organic EL material is formed on the element substrate 122.

<Transfer of Gas Barrier Film> Next, the mask is removed from the element substrate 122 on which the organic EL element 124 is formed. An acrylic adhesive is applied onto the masked element substrate 122. Then, the protective film 26 is peeled off from the gas barrier film 10a of the first embodiment, and the inorganic layer 16 is bonded to the gas barrier film 10a toward the surface of the adhesive, and then the substrate of the gas barrier film 10a is peeled off to prepare an organic EL laminate. 120a.

[Example 26] After the masking was removed, the element substrate 122 on which the organic EL element 124 was formed was loaded in a general plasma CVD apparatus, and a thickness of 1500 nm composed of tantalum nitride was formed by plasma CVD (CCP-CVD). An organic EL laminate 120c as shown in Fig. 7(C) was produced in the same manner as in Example 25 except for the passivation film 126.

[Example 27] An organic EL laminate 124 was produced in the same manner as in Example 25 except that the gas barrier film 10a of Example 1 was used as the element substrate 122. Specifically, the gas barrier film 10a of the first embodiment was transferred to a TAC film with an adhesive layer of an optical adhesive film (manufactured by PDS1 PANAC Corporation) bonded to FUJITAC (manufactured by TD80 Fujifilm Corporation), and the substrate 12 was bonded. The laminated body which has been peeled off is used as the element substrate 122. Moreover, the organic EL element 124 is formed on the peeling resin layer 20 of the element substrate 122. Then, the organic EL element 124 was sealed with another gas barrier film 10a in the same manner as described above to produce the organic EL laminate 124.

[Evaluation] The durability of the organic EL laminates of Examples 25 to 27 produced was evaluated.

Specifically, the produced organic EL laminate 124 was allowed to stand for 200 hours in an environment of a temperature of 60 ° C and a humidity of 90% RH. After standing, a voltage of 7 V was applied to each of the organic EL laminates 124 by a SMU 2400 type source measuring unit manufactured by Keithlel Co., Ltd. to emit light. Observation was made from the side of the gas barrier film 10a by a microscope to confirm the presence or absence of dark spots, and the evaluation was performed based on the following criteria. A: No occurrence of black spots was observed at all B: A small amount of dark spots C was observed: C was clearly observed to be produced D: The area ratio of dark spots was large, and the results of Examples 25 to 27 were evaluated. The organic EL laminates were all A. Based on the above results, the effects of the present invention are apparent.

10‧‧‧ gas barrier film
12‧‧‧Substrate
14‧‧‧Organic layer
16‧‧‧Inorganic layer
18‧‧‧ gas barrier
20‧‧‧ peeling resin layer
24‧‧‧Organic protective layer
26‧‧‧Protective film
30‧‧‧Transfer layer
40‧‧‧ Coating Department
42‧‧‧Drying Department
44‧‧‧ Hardening Department
48‧‧‧Transport roller pair
50‧‧‧Supply room
50a, 52a, 54a‧‧‧ vacuum evacuation means
52‧‧‧ Filming room
54‧‧‧The take-up room
58, 60, 76‧‧ ‧ guide rollers
62‧‧‧Roller
64‧‧‧Spray head electrode
68‧‧‧Material Gas Supply Department
70‧‧‧High frequency power supply
72‧‧‧Laminating roller pair
100‧‧‧ wavelength conversion film
102‧‧‧wavelength conversion layer
104‧‧‧ gas barrier film
110‧‧‧ phase difference film with gas barrier
112‧‧‧ phase difference film
120‧‧‧Organic EL laminate
122‧‧‧ element substrate
124‧‧‧Organic EL components
126‧‧‧passivation film

Fig. 1(A) is a view schematically showing an example of a gas barrier film of the present invention, and Fig. 1(B) is a view schematically showing a state in which a substrate is peeled off from the gas barrier film of Fig. 1(A). 2(A) and 2(B) are views schematically showing another example of the gas barrier film of the present invention. Fig. 3 is a view schematically showing another example of the gas barrier film of the present invention. 4(A) to 4(C) are schematic views for explaining a transfer method of the gas barrier film of the present invention. Fig. 5 is a view schematically showing an example of a retardation film with a gas barrier layer of the present invention. Fig. 6 is a view schematically showing an example of a wavelength conversion film of the present invention. 7(A) to 7(C) are diagrams each showing an example of the organic EL laminate of the present invention. 8(A) and 8(B) are views schematically showing an example of a film forming apparatus for producing a gas barrier film of the present invention.

10a‧‧‧ gas barrier film

12‧‧‧Substrate

14‧‧‧Organic layer

16‧‧‧Inorganic layer

18‧‧‧ gas barrier

20‧‧‧ peeling resin layer

30‧‧‧Transfer layer

Claims (24)

A gas barrier film comprising: a substrate; a gas barrier layer provided on one surface side of the substrate, having a combination of a plurality of inorganic layers and an organic layer forming a surface of the inorganic layer; and a release resin And a layer disposed between the substrate and the gas barrier layer, adhered to the organic layer, and used to peel off the substrate and the gas barrier layer. The gas barrier film according to claim 1, wherein the release resin layer is thicker than the organic layer. The gas barrier film according to claim 1 or 2, wherein the material for forming the release resin layer is a cyclic olefin resin having a glass transition temperature Tg of 100 ° C or more. The gas barrier film according to claim 3, wherein the material for forming the release resin layer is a cyclic olefin copolymer. The gas barrier film according to claim 1 or 2, wherein the peeling resin layer has a thickness of 0.1 to 25 μm. The gas barrier film according to claim 1 or 2, wherein the inorganic layer forming material is tantalum nitride, cerium oxide, or a mixture thereof. The gas barrier film according to claim 1 or 2, wherein the material for forming the organic layer is an ultraviolet curable resin or an electron beam curable resin, and the glass transition temperature Tg after curing is 200 ° C or higher. The gas barrier film according to claim 7, wherein the material for forming the organic layer contains 5% or more and less than 50% of a monofunctional or higher acrylate having an adamantane skeleton. The gas barrier film according to claim 7, wherein the material for forming the organic layer contains 5% or more and less than 50% of a bifunctional or higher acrylate having an anthracene skeleton. The gas barrier film according to claim 1 or 2, wherein the organic layer has a thickness of 0.1 to 5 μm. The gas barrier film according to claim 1 or 2, further comprising a protective film or an organic protective layer provided on the gas barrier layer. The gas barrier film according to claim 11, wherein the organic protective layer is an acrylic adhesive. The gas barrier film of claim 11, further comprising a protective film disposed on the organic protective layer. The gas barrier film according to claim 11, wherein the organic protective layer has a thickness of 0.1 to 50 μm. The gas barrier film according to claim 1 or 2, wherein the substrate is a polyethylene terephthalate film to which a release layer is applied. The gas barrier film according to claim 1 or 2, wherein a water vapor transmission rate of the structure in which the substrate is removed is less than 0.01 g/(m ² day). The gas barrier film according to claim 1 or 2, wherein the structure in which the substrate is removed has a visible light transmittance of 85% or more and a retardation value of 30 nm or less. A method of transferring a gas barrier film, wherein a transfer layer having a gas barrier layer and a release resin layer is transferred to a transfer target, wherein the gas barrier film according to any one of claims 1 to 17 The surface on the opposite side of the substrate is attached to the object to be transferred, and the substrate is peeled off. The method of transferring a gas barrier film according to claim 18, wherein the object to be transferred is any one of a wavelength conversion material, a retardation film, an organic EL element, and a passivation film formed on the organic EL element. . A wavelength conversion film having: a wavelength conversion layer; and a transfer layer laminated on the wavelength conversion layer, and having the gas barrier film according to any one of claims 1 to 17 removed from the substrate The gas barrier layer and the aforementioned release resin layer. A retardation film having a gas barrier layer, comprising: a retardation film; and a transfer layer laminated on the retardation film, and having the gas barrier film according to any one of claims 1 to 17 The gas barrier layer of the substrate and the release resin layer are removed. An organic EL laminate comprising: an organic EL device; and a transfer layer laminated on the organic EL device, and having the gas barrier film according to any one of claims 1 to 17 removed from the substrate The aforementioned gas barrier layer and the aforementioned release resin layer. The organic EL laminate according to claim 22, wherein a passivation film is provided between the organic EL element and the transfer layer. The organic EL laminate according to claim 22, further comprising an element substrate supporting the organic EL element, wherein the element substrate includes a transfer layer, and the transfer layer is provided in items 1 to 17 of the patent application scope. The gas barrier film according to any one of the above, wherein the gas barrier layer of the substrate and the release resin layer are removed.