KR102103091B1 - Gas barrier film, transfer method of gas barrier film, wavelength conversion film, retardation film with gas barrier layer, and organic EL laminate - Google Patents

Abstract

A thin, transferable, and gas barrier film having a high gas barrier property even after transfer is provided, and a method for transferring the gas barrier film is also provided, and a wavelength conversion film, a phase difference film with a gas barrier layer, and an organic EL lamination using the gas barrier film Sieve. The gas barrier film is provided between a substrate and a gas barrier layer and a gas barrier layer having at least one set of a combination of an inorganic layer provided on one side of the substrate and the substrate and an organic layer serving as the formation surface of the inorganic layer, and the organic layer and It adheres and has a release resin layer for peeling with the substrate.

Description

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

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

In recent years, in organic EL devices (organic electroluminescence devices), solar cells, devices or display materials such as quantum dot films, packaging materials such as sap bags containing chemicals deteriorated by moisture or oxygen, High gas barrier properties are required.

For this reason, in these members, the gas barrier film is stuck or sealed with a gas barrier film in order to provide the necessary gas barrier properties.

In order to use a gas barrier film in a field where high gas barrier properties are required, Patent Document 1, as a method of improving gas barrier properties, uses a gas barrier layer as an inorganic layer, a gas barrier layer as a multilayer structure, and It is described that a gas barrier layer is formed on a resin film having a high glass transition temperature Tg.

Gas barrier films having high gas barrier properties have been developed in various electronic devices and functional films, making it possible to seal materials that have been difficult to seal in the past.

For example, in Patent Document 2, as a quantum dot film used in a backlight unit such as an LCD, a quantum dot layer (QD phosphor material film layer) is sandwiched between two gas barrier films to protect quantum dots, and is of a laminated type. Quantum dot films are described.

In addition, Patent Document 3 describes that an organic EL element is sealed using a gas barrier film.

By using a gas barrier film having a high gas barrier property in this way, it is possible to reduce the thickness, weight, and flexibility of various electronic devices such as displays. Therefore, if the gas barrier film can be further thinned, further thinning, weight reduction, and the like of the electronic device can be performed.

As described in Patent Literature 1 and the like, such a gas barrier film has a configuration in which a gas barrier layer is formed on the substrate using a resin film as a substrate. For this reason, in order to make the gas barrier film thin, it is conceivable to thin the substrate.

Here, the gas barrier layer having high gas barrier properties is a thin inorganic layer. For this reason, the gas barrier layer is liable to crack even by minute buckling or contact, and when cracked, performance deteriorates. For this reason, when laminating a gas barrier layer on a thin substrate, it is necessary to stabilize the transport so that the substrate can be prevented from buckling.

In Patent Document 4, the self-supporting property of the substrate can be secured by attaching a protective material to the back side of the substrate, and even when a thin substrate is used, a gas barrier layer can be appropriately formed without causing buckling of the substrate. What can be described is described.

By using such a method, it is possible to form a gas barrier layer on a thin substrate of about several tens of μm. However, when it becomes thinner than this, it becomes difficult to attach a protective material for reinforcement to this substrate while conveying the thin substrate.

As a method of solving the problem associated with thinning of such a gas barrier film, a transfer method has been proposed in which only the gas barrier layer is transferred to a sealing object (object to be transferred).

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 body.

United States Patent Publication No. 5654084 Japanese Patent Publication No. 2013-544018 Japanese Patent Publication No. 2014-197537 Japanese Patent Application Publication No. 2015-66812 Japanese Patent Application Publication No. 2007-118564

As described above, in order to realize high gas barrier properties, there is a configuration in which an inorganic layer is used as the gas barrier layer.

Here, according to the examination of the inventors, in the gas barrier film of the transfer method in which the gas barrier layer described in Patent Document 5 is peeled from the substrate and transferred to the object to be transferred, when the gas barrier layer and the substrate are peeled, the gas barrier Since a shearing force is applied to the layer, it was found that the inorganic layer is cracked by this shearing force, and the gas barrier layer after transfer may not be able to express sufficient gas barrier properties.

An object of the present invention is to solve the problems of the prior art, and provides a gas barrier film and a gas barrier film transfer method that is thin, transferable and has a high gas barrier property even after transfer. It is to provide a wavelength conversion film using a barrier film, a retardation film with a gas barrier layer, and an organic EL laminate.

As a result of earnest research in order to achieve the above object, the present inventor has provided a substrate, a gas barrier layer provided on one side of the substrate, and having at least one set of a combination of an inorganic layer and an organic layer serving as a formation surface of the inorganic layer, and a substrate It was found that the above-mentioned problems can be solved by providing a release resin layer for providing a gap between the gas barrier layer and the organic layer and adhering to the substrate and the gas barrier layer, thereby completing the present invention.

That is, the present invention provides a gas barrier film and a gas barrier film production method having the following constitution, a wavelength conversion film using the gas barrier film, a retardation film with a gas barrier layer, and an organic EL laminate.

(1) a substrate,

A gas barrier layer provided on one side of the substrate and having at least one set of a combination of an inorganic layer and an organic layer serving as a formation surface of the inorganic layer,

A gas barrier film provided between the substrate and the gas barrier layer, in close contact with the organic layer, and having a release resin layer for peeling 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 higher.

(4) The gas barrier film according to (3), in which the material for forming the release resin layer is a cycloolefin copolymer.

(5) The gas barrier film according to any one of (1) to (4), wherein the release 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 material for forming the inorganic layer is silicon nitride, silicon 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 cured resin, and the glass transition temperature Tg after curing is 200 ° C or higher.

(8) The gas barrier film according to (7), wherein the material for forming the organic layer contains 5% by weight or more and less than 50% by weight of at least one acrylate having an adamantane skeleton.

(9) The gas barrier film according to (7), wherein the material for forming the organic layer contains 5% by weight or more and less than 50% by weight of a bifunctional or higher acrylate having a fluorene skeleton.

(10) The gas barrier film according to any one of (1) to (9), wherein the thickness of the organic layer is 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 thickness of the organic protective layer is 0.1 to 50 μm.

(15) The gas barrier film according to any one of (1) to (14), wherein the substrate is a polyethylene terephthalate film provided with a release layer.

(16) The gas barrier film according to any one of (1) to (15), wherein the water vapor transmittance of the structure in which the substrate is removed is less than 0.01 g / (m ² · day).

(17) The gas barrier film according to any one of (1) to (16), wherein the visible light transmittance of the structure in which the substrate is removed is 85% or more and the retardation value is 30 nm or less.

(18) As a transfer method of a gas barrier film for transferring a transfer layer comprising a gas barrier layer and a release resin layer to an object to be transferred, as opposed to the substrate of the gas barrier film described in any one of (1) to (17). The gas barrier film transfer method of sticking the side surface to the object to be transferred and peeling the substrate.

(19) The method for transferring the gas barrier film according to (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.

(20) a wavelength conversion layer,

A wavelength conversion film having a transfer layer comprising a gas barrier layer and a release resin layer, the substrate being removed from the gas barrier film according to any one of (1) to (17), laminated on the wavelength conversion layer.

(21) a retardation film,

A retardation film with a gas barrier layer having a transfer layer comprising a gas barrier layer and a release resin layer, the substrate being removed from the gas barrier film according to any one of (1) to (17), laminated on the retardation film.

(22) an organic EL element,

An organic EL laminate having a transfer layer comprising a gas barrier layer and a release resin layer, which has a substrate removed from the gas barrier film according to any one of (1) to (17), laminated on an organic EL element.

(23) The organic EL laminate according to (22), having a passivation film between the organic EL element and the transfer layer.

(24) A device substrate further supporting an organic EL device, wherein the device substrate is provided with a gas barrier layer and a release resin layer from which the substrate is removed from the gas barrier film described in any one of (1) to (17). The organic EL laminate according to (22) or (23) comprising a transfer layer.

According to the present invention as described above, a gas barrier film and a gas barrier film production method that is thin, transferable and has high gas barrier properties even after transfer, a wavelength conversion film using the gas barrier film, and a phase difference film with a gas barrier layer And an organic EL laminate.

In Fig. 1, Fig. 1 (A) is a diagram conceptually showing an example of the gas barrier film of the present invention, and Fig. 1 (B) shows a state in which the substrate is peeled from the gas barrier film in Fig. 1 (A). It is a conceptual diagram.
In FIG. 2, FIGS. 2 (A) and 2 (B) are diagrams conceptually showing another example of the gas barrier film of the present invention.
3 is a diagram conceptually showing another example of the gas barrier film of the present invention.
In FIG. 4, FIGS. 4 (A) to 4 (C) are conceptual views for explaining the method for transferring the gas barrier film of the present invention.
5 is a diagram conceptually showing an example of a retardation film with a gas barrier layer according to the present invention.
6 is a diagram conceptually showing an example of the wavelength conversion film of the present invention.
In Fig. 7, Figs. 7 (A) to 7 (C) are diagrams conceptually showing an example of the organic EL laminate of the present invention.
In FIG. 8, FIGS. 8 (A) and 8 (B) are diagrams conceptually showing an example of a film forming apparatus for producing the gas barrier film of the present invention.

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

The gas barrier film of the present invention is provided between a substrate and a gas barrier layer provided on one side of the substrate and having at least one set of a combination of an inorganic layer and an organic layer which is the formation surface of the inorganic layer, and the substrate and the gas barrier layer. It is a gas barrier film provided, in close contact with the organic layer, and having a release resin layer for peeling from the substrate. This gas barrier film is used by peeling only the substrate and transferring the transfer layer including the gas barrier layer and the peeling resin layer to the object to be transferred.

1 (A) conceptually shows an example of the gas barrier film of the present invention.

The gas barrier film 10a shown in FIG. 1A is basically a gas barrier layer having a substrate 12 and an organic layer 14 and an inorganic layer 16, which are stacked on one surface of the substrate 12. (18) and a release resin layer (20) laminated between the substrate (12) and the gas barrier layer (18).

Further, as shown in Fig. 1 (A), the gas barrier layer 18 is stacked with the organic layer 14 facing the release resin layer 20 side, and the inorganic layer 16 is on the organic layer 14. Stacked. 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 in close contact with the organic layer 14 and further, the substrate 12 at the interface with the substrate 12 ) And peelable. That is, the peeling force (adhesion force) between the organic layer 14 and the peeling resin layer 20 is greater than the peeling force between the substrate 12 and the peeling resin layer 20.

Thereby, the gas barrier film 10a peels only the substrate 12, and the transfer layer 30 including the gas barrier layer 18 and the peeling resin layer 20 can be transferred to the object to be sealed. have.

In addition, the transfer of the transfer layer 30 to the transfer object is basically carried out by bonding the gas barrier layer 18 side of the gas barrier film 10a to the transfer object, and then from the gas barrier film 10a to the substrate 12 ) To transfer the transfer layer 30 to the transfer body, but after peeling the substrate 12 from the gas barrier film 10a to take out the transfer layer 30, the transfer layer 30 is transferred. You may stick to

As described above, as a thinner gas barrier film, a gas barrier film of a transfer method has been proposed in which a release layer is formed between the substrate and the gas barrier layer, and the gas barrier layer is peeled off the substrate and transferred to the object to be transferred.

However, according to the examination of the present inventors, in such a gas barrier film of the transfer method, when the gas barrier layer and the substrate are peeled off, a shear force is applied to the gas barrier layer, and the inorganic layer is cracked by this shear force. It has been found that the gas barrier layer after transfer may not be able to express sufficient gas barrier properties.

On the other hand, in the present invention, as the base of the inorganic layer 16 that exhibits gas barrier properties, an organic layer 14 is provided, and between the organic layer 14 and the substrate 12, a release resin layer (20), and the release resin layer 20 is configured to be in close contact with the organic layer 14 and to be peelable from the substrate 12 at the interface with the substrate 12.

At the time of peeling, by peeling at the interface between the peeling resin layer 20 and the substrate 12, the peeling resin layer 20 existing between the inorganic layer 16 and the peeling surface becomes a stress relaxation layer, and the substrate 12 ), It is possible to prevent the inorganic layer 16 from cracking due to the shear force applied when peeling.

Here, as described above, the peeling resin layer 20 needs to adjust the peeling force so as to peel at the interface with the substrate 12, and also needs to have a function as a stress relaxation layer. For this reason, it is difficult to make it 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, the layer serving as the base of the inorganic layer 16 needs to have a suitable hardness and have higher heat resistance.

For this reason, in the case where the organic layer 14 is not provided between the release resin layer 20 and the inorganic layer 16, that is, when the inorganic layer 16 is directly formed on the release resin layer 20, In, the inorganic layer 16 cannot be formed appropriately, and high gas barrier properties cannot be obtained.

On the other hand, the gas barrier film of the present invention has an organic layer 14 on the release resin layer 20 as the formation surface of the inorganic layer 16, and thus a suitable base layer is provided. For this reason, the inorganic layer 16 can be appropriately formed, and high gas barrier properties can be obtained.

In addition, it is preferable that the gas barrier film of the present invention further has a protective film on the gas barrier layer 18 for protecting the gas barrier layer 18 (more specifically, the inorganic layer 16).

By having a protective film, it is possible to prevent the inorganic layer 16 from cracking during transport or winding of the gas barrier film.

In addition, when the gas barrier film has a protective film, the protective film may be peeled off to expose the gas barrier layer 18 and then transferred to the object to be transferred.

Moreover, like the gas barrier film 10b shown in FIG. 2 (A), the organic protection for protecting the gas barrier layer 18 on the gas barrier layer 18 (more specifically, the inorganic layer 16) It is also desirable to have a layer 24.

By having the organic protective layer 24, it is possible to prevent the inorganic layer 16 from cracking during transport or winding of the gas barrier film.

In addition, in the case of having the organic protective layer 24, 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, The peeling resin layer 20 and the gas barrier layer 18 are transferred to the object to be transferred.

Moreover, the organic protective layer 24 may be an adhesive layer having adhesiveness.

Since the organic protective layer 24 has tackiness, when the transfer layer 30 is transferred to an object to be transferred, transfer can be performed easily without applying an adhesive or the like.

Moreover, like the gas barrier film 10c shown in FIG. 2 (B), it has the organic protective layer 24 on the gas barrier layer 18, and also the protective film 26 on the organic protective layer 24 You may have

By having the organic protective layer 24 and the protective film 26, it is possible to prevent the inorganic layer 16 from cracking during transport or winding of the gas barrier film.

Moreover, when the organic protective layer 24 is an adhesive layer, by having the protective film 26, conveyance and winding of a gas barrier film can be facilitated, and a foreign material etc. adheres to the adhesive layer, or adhesiveness It can be prevented from being deteriorated.

In addition, in the example shown in FIG. 1 (A), the gas barrier layer 18 is configured to have one layer of the organic layer 14 and one layer of the inorganic layer 16, but the organic layer is not limited to this. And one or more inorganic layers, or two or more sets of the inorganic layer 16 and the organic layer 14 serving as a base layer of the inorganic layer 16.

For example, in the gas barrier film 10d shown in FIG. 3, the organic layer 14, the inorganic layer 16, the organic layer 14, and the inorganic layer 16 are in this order on the release resin layer 20. It has a gas barrier layer 18 formed of. That is, the gas barrier layer 18 of the gas barrier film 10d has a configuration having two sets of a combination of the organic layer 14 and the inorganic layer 16.

Thus, by having two or more sets of the organic layer 14 and the inorganic layer 16 in combination, the gas barrier property can be further improved.

Here, in the gas barrier film of the present invention, the water vapor transmittance of the structure in which the substrate 12 is removed from the gas barrier film is preferably less than 0.01 [g / (m ² · day)], and 0.005 [g / ( m ² · day)] or less, more preferably 0.001 [g / (m ² · day)] or less. For example, when the gas barrier film is composed of a substrate 12, a gas barrier layer 18, and a release resin layer 20, the configuration in which the substrate 12 is removed from the gas barrier film is a gas barrier layer ( 18) and a transfer layer 30 made of a release resin layer 20. In addition, when the gas barrier film is composed of a substrate 12, a gas barrier layer 18, a release resin layer 20, and an organic protective layer 24, with the configuration in which the substrate 12 is removed from the gas barrier film , It means a transfer layer 30 made of a gas barrier layer 18, a release resin layer 20, and an organic protective layer 24.

It is preferable that the gas barrier film of the present invention has a low water vapor transmission rate.

Even if the gas barrier film of the present invention is a transfer layer 30 having a high gas barrier property, it is possible to transfer appropriately while preventing cracks or the like of the inorganic layer 16 and maintaining a high gas barrier property.

Moreover, in the gas barrier film of this invention, it is preferable that the visible light transmittance of the structure which removed the board | substrate 12 from this gas barrier film is 85% or more. Moreover, it is preferable that the retardation value of the transfer layer 30 is 30 nm or less.

When the visible light transmittance and retardation value of the transfer layer 30 are within the above range, the gas barrier film of the present invention is transferred to seal a wavelength conversion layer such as a quantum dot film or an optical member such as an organic EL element. Alternatively, in the case of imparting gas barrier properties to an optical film such as a retardation film, sealing of the optical member or imparting gas barrier properties can be performed without affecting the optical performance of these objects.

Next, the material and configuration of each component of the gas barrier film of the present invention will be described. Hereinafter, the gas barrier films 10a to 10d may be collectively referred to as the “gas barrier film 10”.

In the gas barrier film 10, the board | substrate 12 can use various and well-known sheet-like thing used as the board | substrate (support) in various gas barrier films and various laminated gas barrier films.

As the substrate 12, specifically, low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), poly Vinyl alcohol (PVA), polyacrylonitrile (PAN), polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, Films (resin films) made of various resin materials, such as polypropylene (PP), polystyrene (PS), ABS, cycloolefin copolymer (COC), cycloolefin polymer (COP), and triacetyl cellulose (TAC) , Suitably illustrated.

In the present invention, on the surface of such a film, a layer (membrane) that expresses the necessary functions, such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light blocking layer, a planarization layer, a buffer layer, a stress relaxation layer, a release layer, etc. You may use what is formed as the board | substrate 12.

Among them, since the elongation at break is high and it is difficult to break at the time of conveyance, it can be made thinner, has a high melting point, has heat resistance, and can easily peel at the interface with the release resin layer 20, From the viewpoint of low cost and the like, as the substrate 12, a PET film having a release layer is preferable. More specifically, it is preferable that a release layer is formed on the surface of the PET film 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 and the forming material.

According to the studies of the present inventors, 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 within the above range, it is preferable in that the mechanical strength of the gas barrier film 10 is sufficiently secured and peeling can be easily performed during transfer.

The organic layer 14 is a layer made of an organic compound, and is basically a polymer (crosslinked) of monomers, oligomers, and the like that form the organic layer 14.

The organic layer 14 is the formation surface of the inorganic layer 16. Specifically, the organic layer 14 mainly functions as a base layer for appropriately forming the inorganic layer 16 that exhibits gas barrier properties in the gas barrier film 10.

By having such an organic layer 14, the surface of the peeling resin layer 20 (or lower layer inorganic layer 16) and the surface of the peeling resin layer 20 (or lower layer inorganic layer 16) The surface for forming the inorganic layer 16 by embedding foreign substances or the like attached to the film can be made into a state suitable for the film formation of the inorganic layer 16. Thereby, the area | region where the inorganic compound which forms the inorganic layer 16, such as the unevenness | corrugation of the surface of the peeling resin layer 20 (or the inorganic layer 16 of the lower layer) or the unevenness | corrugation by adhesion of a foreign material, is difficult to remove is removed. , It is possible to form an appropriate inorganic layer 16 on the entire surface of the release resin layer 20 (or the lower inorganic layer 16) without a gap, and the inorganic layer 16 having high gas barrier properties Can form.

Moreover, it is preferable that the glass transition temperature Tg of the organic layer 14 is higher than the glass transition temperature Tg of the release resin layer 20, and it is preferable that it is 200 degreeC or more.

By setting the organic layer 14 having a high heat resistance having a glass transition temperature Tg of 200 ° C or higher, it is possible to appropriately form the inorganic layer 16.

Moreover, it is preferable that the organic layer 14 has moderate flexibility in order to prevent the inorganic layer 16 from cracking or the like.

Note that 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, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluorine resin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate , Polyurethane, polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester , Thermoplastic resins such as acrylic compounds; A film of polysiloxane or other organosilicon compounds is suitably exemplified. These may use a plurality.

Among them, the organic layer 14 composed of a polymer of a radically curable compound and / or a cationically curable compound having an ether group as a functional group is suitable from the viewpoint of excellent glass transition temperature or strength.

Among them, acrylic resins and methacrylic resins mainly composed of polymers of monomers and oligomers of acrylates and / or methacrylates are mainly composed of organic layers (in terms of low refractive index, high transparency, and excellent optical properties). 14).

Especially, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resins and methacrylic resins mainly composed of polymers such as monomers and oligomers of bifunctional or higher, especially trifunctional or higher acrylate and / or methacrylate are exemplified as appropriate. Moreover, it is also preferable to use two or more of these acrylic resins and methacrylic resins.

Here, it is preferable that the material for forming the organic layer 14 is an ultraviolet curing resin or an electron beam curing resin.

By using an ultraviolet curing resin or an electron beam curing 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 a strong peeling force can be realized. You can. Therefore, it can be set as the structure which peels the gas barrier film 10 at the interface of the peeling resin layer 20 and the board | substrate 12.

In addition, the material for forming the organic layer 14 is a resin material containing 5% by weight or more and less than 50% by weight of a monofunctional or higher acrylate having an adamantane skeleton, or a bifunctional or higher acrylate having a fluorene skeleton. It is preferable that it is a resin material containing 5% by weight or more and less than 50% by weight.

As a material for forming the organic layer 14, a high glass transition temperature Tg was maintained by using a resin material containing a monofunctional or higher acrylate having an adamantane skeleton or a bifunctional or higher acrylate having a fluorene skeleton. The shrinkage rate at the time of curing shrinkage can be lowered, and the inorganic layer 16 formed on the organic layer 14 can be prevented from cracking.

The organic layer 14 may be formed (deposited) by a known method of forming a layer made of an organic compound according to the organic layer 14 to be formed. As an example, a coating method is exemplified.

The organic layer 14 prepares a coating composition containing, for example, an organic solvent, an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.) to be the organic layer 14, and a crosslinking agent, to prepare the coating composition. It can be formed by coating on the release resin layer 20 to form a coating film, and drying and curing the coating film.

By forming by a coating method, a thin organic layer 14 is obtained.

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

The inorganic layer 16 is a layer made of an inorganic compound.

In the gas barrier film 10, the target gas barrier property is mainly expressed by the inorganic layer 16.

The material for forming the inorganic layer 16 is not limited, and a layer made of an inorganic compound that exhibits gas barrier properties can be used in various ways.

Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, and indium tin oxide (ITO); Metal nitrides such as aluminum nitride; Metal carbides such as aluminum carbide; Silicon oxides such as silicon oxide, silicon oxynitride, silicon oxycarbide, and silicon oxynitride carbide; Silicon nitride such as silicon nitride and silicon carbide; Silicon carbide such as silicon carbide; Hydrides of these; Mixtures of two or more of these; And their hydrogen content; A film made of an inorganic compound such as is preferably exemplified. Moreover, mixtures of two or more of these can also be used.

Particularly, metal oxides and nitrides, specifically, silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and mixtures of two or more of them, are highly transparent and can exhibit excellent gas barrier properties. Is used. Among these, silicon nitride, silicon oxide, and mixtures thereof are more suitably used because of their high transparency and high flexibility in addition to excellent gas barrier properties.

The formation of such an inorganic layer 16 is dependent on the material for forming the inorganic layer 16, CCP-CVD (capacity coupled plasma chemical vapor deposition method), ICP-CVD (inductively coupled plasma chemical vapor deposition method), sputtering, It may be performed by a known vapor phase film deposition method such as vacuum deposition.

The film thickness of the inorganic layer 16 may be appropriately determined depending on the material to be formed, a thickness capable of expressing a desired gas barrier property. According to the studies of the inventors, the thickness of the inorganic layer 16 is preferably 10 to 200 nm, more preferably 15 to 100 nm, and particularly preferably 20 to 75 nm.

When the thickness of the inorganic layer 16 is 10 nm or more, sufficient gas barrier performance is stably exhibited. In addition, the inorganic layer 16 is generally brittle, and if it is too thick, cracks, cracks, peeling, and the like may occur. However, cracks are generated when the thickness of the inorganic layer 16 is 200 nm or less. Can be prevented.

In addition, when the gas barrier film 10 has a plurality of inorganic layers 16, the thickness of each inorganic layer 16 may be the same or different. Moreover, the formation material of each inorganic layer 16 may be same or different.

In the gas barrier film 10, the release resin layer 20 is provided between the substrate 12 and the organic layer 14.

As described above, the release resin layer 20 is a resin layer that is in close contact with the organic layer 14 and can be peeled from the substrate 12 at the interface with the substrate 12. The release resin layer 20 separates the substrate 12 and the gas barrier layer 18. The release resin layer 20 is a layer that also functions as a stress relaxation layer that suppresses the application of shear force to the inorganic layer 16 when the substrate 12 is peeled off. Moreover, after peeling of the board | substrate 12, the peeling resin layer 20 also functions as a support body.

It is preferable that the peeling resin layer 20 has low water content and high heat resistance.

As described above, the inorganic layer 16 that exhibits high gas barrier properties is formed by vacuum deposition such as plasma CVD. If the water-repellent resin layer 20 has a high water content, even if vacuuming is performed, since moisture is released, the degree of vacuum cannot be increased, and there is a fear that the inorganic layer 16 cannot be formed. Further, even when the inorganic layer 16 is formed, when the release resin layer 20 expands and contracts due to absorption and release of moisture, there is a fear that the inorganic layer 16 may crack, and thus a high gas barrier property cannot be obtained. have. Therefore, it is preferable that the release resin layer 20 has a low water content. Further, it is preferable that the heat resistance is high in order to form the inorganic layer 16 by plasma CVD or the like.

From the viewpoints of adhesion, moisture, and heat resistance to the substrate 12 and the organic layer 14, examples of the material for forming the release resin layer 20 include glass such as cycloolefin copolymer (COC) and cycloolefin polymer (COP). It is preferable that the transition temperature Tg is a cyclic olefin resin of 100 ° C or higher.

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

Such release resin layer 20 can be formed by the coating method similar to the organic layer 14, for example.

By forming by the coating method, a thin release resin layer 20 is obtained.

The thickness of the release resin layer 20 may be appropriately set depending on the forming material of the release resin layer 20, the characteristics of the organic layer 14, the inorganic layer 16, and the substrate 12. According to the studies of the present inventors, 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.

By setting the thickness of the release resin layer 20 to 0.1 μm or more, adhesion between the substrate 12 and the organic layer 14 can be appropriately controlled, and peeling at the interface with the substrate 12 can be facilitated. In addition, the shear force applied to the inorganic layer 16 at the time of peeling of the substrate 12 can be reduced to prevent the inorganic layer 16 from cracking.

In addition, when the thickness of the release resin layer 20 is 25 μm or less, problems such as cracks in the release resin layer 20 and curling of the gas barrier film 10 due to the release resin layer 20 being too thick Generation can be suitably suppressed, and the gas barrier film 10 can be easily rolled up in a roll shape.

Moreover, from the viewpoint of stress relaxation when peeling the substrate 12, the hardness of the release resin layer 20 is preferably lower than the hardness of the organic layer 14, and also Young's of the release resin layer 20 The modulus) is preferably lower than the Young's modulus of the organic layer 14. That is, it is preferable that the release resin layer 20 is softer than the organic layer 14.

Here, it is preferable that the thickness of the release resin layer 20 is thicker than the thickness of the organic layer 14.

As described above, it is preferable that the organic layer 14 serving as the base layer of the inorganic layer 16 has higher heat resistance. Therefore, it is preferable to use a material having a higher 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 becomes hard and difficult to elongate, so that the thickness of the soft organic resin layer 14 is made thin and the thickness of the soft release resin layer 20 is increased. Since the base layer 20 can function properly as a stress relaxation layer, the crack of the inorganic layer 16 when peeling off the board | substrate 12 is prevented, and high gas barrier property can be obtained.

Moreover, the peeling force of the peeling resin layer 20 and the board | 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, If it is higher than the peeling force of the release resin layer 20 and the substrate 12, there is no limitation.

The peeling force between the release resin layer 20 and the substrate 12 is preferably 0.04 N / 25 mm to 1 N / 25 mm.

By setting the peeling force between the peeling resin layer 20 and the substrate 12 within the above range, peeling off during transportation due to the weak peeling force can be suppressed. When peeling off 12), problems such as damaging the inorganic layer 16 and deformation of the gas barrier film 10 can be suppressed.

In addition, peeling force (sticking force) may be measured according to the 180 ° peeling test method of JIS Z 0237.

The organic protective layer 24 is a layer made of an organic compound, and is formed on the gas barrier layer 18 (more specifically, the inorganic layer 16) to protect 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 the organic layer 14 can be used.

When the organic protective layer 24 is an adhesive layer, the forming material is not limited, and various known adhesive materials can be used.

From the viewpoint of optical properties, particularly retardation or haze, it is preferable to use an acrylic pressure-sensitive adhesive as the pressure-sensitive adhesive material.

As an acrylic adhesive, SK Dyne series (made by Soken Chemical Co., Ltd.) etc. are illustrated.

The thickness of the organic protective layer 24 may be appropriately set depending on the material of the organic protective layer 24 and the characteristics of the inorganic layer 16. According to the studies of the inventors, 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.

When the thickness of the organic protective layer 24 is 0.1 μm or more, the inorganic layer 16 can be appropriately protected. In addition, by setting the thickness of the organic protective layer 24 to 50 μm or less, it is possible to improve workability when the gas barrier film 10 is adhered to the object to be transferred.

As for the protective film 26, various well-known sheet-shaped objects used as a well-known protective film can be used.

As an example, a film (resin film) made of various resin materials exemplified by the above-described substrate 12 is suitably illustrated.

When the protective film 26 is formed on the surface of the gas barrier layer 18 (more specifically, the inorganic layer 16), the forming material of the protective film 26 preferably has a Young's modulus of 6 GPa or less. . In this case, the protective film 26 is affixed on the inorganic layer 16 which becomes the uppermost layer of the gas barrier layer 18 of the gas barrier film 10, and when transferring the gas barrier film 10, the inorganic It is peeled off from the layer 16 and used. By setting the Young's modulus of the material for forming the protective film 26 to 6 GPa or less, damage to the inorganic layer 16 when peeling the protective film 26 can be more suitably prevented, and high gas barrier properties are obtained. You can. In view of this, LDPE, HDPE, PP, PET, PEN, PVC, PI and the like are suitably exemplified as the material for forming the protective film 26.

The thickness of the protective film 26 may be appropriately set depending on the thickness required for the gas barrier film 10, the Young's modulus of the material for forming the protective film 26, and the like.

According to the examination of the present inventors, the thickness of the protective film 26 is preferably 10 to 300 μm, and more preferably 30 to 50 μm.

By setting the thickness of the protective film 26 to 10 µm or more, it is possible to appropriately prevent damage to the inorganic layer 16 due to impact or the like from the outside during winding, and to suppress wrinkles and deformation during transportation. It is preferable in terms of things.

The thickness of the protective film 26 is preferably 300 μm or less in view of preventing the gas barrier film 10 from being unnecessarily thickened.

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

Next, the 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 transfer method of the gas barrier film of the present invention, the transfer layer including the gas barrier layer and the release resin layer is transferred by attaching the surface on the opposite side of the substrate of the gas barrier film to the transfer body and peeling off the substrate. To warrior.

Hereinafter, the transfer method of the present invention will be described with reference to FIGS. 4 (A) to 4 (C) and FIG. 5.

4 (A) to 4 (C) are gas barrier films using the gas barrier film 10b having the organic protective layer 24 as the adhesive layer shown in FIG. 2 (A), and this gas barrier It shows an example of transferring the film 10b to the retardation film 112 as an image transfer object.

First, as shown in FIG. 4 (A) and FIG. 4 (B), the surface of the gas barrier film 10b on the opposite side to the substrate 12, that is, the organic protective layer 24 side, is a retardation film. (112) It faces and sticks together.

The method of bonding is not limited, and various known methods of bonding a film-like material can be used. In addition, such bonding may be performed in a single-leaf type, and bonding is performed by roll-to-roll (hereinafter also referred to as R to R) using a long gas barrier film 10b and a retardation film 112. You may do it.

Moreover, in the example of illustration, although the gas barrier film 10b was made into the structure which has an adhesive layer, it is not limited to this, Before apply | bonding with the gas barrier film 10b, an adhesive is applied to a to-be-transferred body, and a gas barrier You may bond with the film 10b.

In addition, 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 before the gas barrier film is adhered to the object to be transferred to the object to be transferred. It is enough to perform affixation to Korea.

Next, as shown in FIG. 4 (C), the substrate 12 is peeled from the gas barrier film 10b bonded to the retardation film 112.

The method of peeling the substrate 12 is not limited, and various methods of peeling a known film-like material can be used.

Moreover, such a peeling of the board | substrate 12 may be performed by single sheet type, or may be performed by R to R.

In this way, the transfer layer 30 of the gas barrier film 10b can be transferred to the phase difference film 112, which is an image transfer object, so that the phase difference film 110 with the gas barrier layer shown in Fig. 5 can be obtained.

The transfer method of the gas barrier film of the present invention can prevent the inorganic layer 16 from cracking when the substrate 12 is peeled off, so that the transfer layer 30 is transferred while maintaining high gas barrier properties. Can be transferred to.

Moreover, since the thickness of the transfer layer 30 can be made very thin, the influence on optical properties such as transparency and retardation value can be reduced.

In addition, in this invention, there is no limitation in the to-be-transferred object which transfers a gas barrier film. Since it has high gas barrier properties, high transparency and excellent optical properties with low retardation, it is suitably used for sealing optical members such as organic EL elements and wavelength conversion materials, which require high gas barrier properties. Moreover, it is also possible to provide high gas barrier properties to various optical films, and to use them as optical film and gas barrier films.

Hereinafter, a member using the gas barrier film of the present invention will be described.

The phase difference film 110 with a gas barrier layer shown in FIG. 5 which is an example of the phase difference film with a gas barrier layer of the present invention using the gas barrier film of the present invention includes an organic protective layer 24, an inorganic layer 16, The transfer layer 30 having the organic layer 14 and the release resin layer 20 has a structure stacked on the retardation film 112.

Since the thickness of the transfer layer 30 is very thin, the retardation film 110 with a gas barrier layer can be made into a film having high gas barrier properties in addition to the optical properties of the retardation film itself while suppressing the increase in thickness. You can.

6 is an example of a wavelength conversion film by transferring the gas barrier film of the present invention and sealing the wavelength conversion layer.

The wavelength conversion film 100 shown in FIG. 6 includes the wavelength conversion layer 102, the gas barrier film 104 laminated on one surface of the wavelength conversion layer 102, and the other surface of the wavelength conversion layer 102. It has a transfer layer 30 laminated on.

The wavelength conversion layer 102 has a function of converting the wavelength of incident light and outputting it, and is, for example, a quantum dot layer formed by dispersing quantum dots in a binder such as resin.

The type of quantum dots contained in the quantum dot layer is not particularly limited, and various known quantum dots may be appropriately selected depending on the required wavelength conversion performance and the like.

The type of the binder contained in the quantum dot layer is not particularly limited, and various known binders may be appropriately selected depending on the type of quantum dots, required performance, and the like.

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

As shown in FIG. 6, the wavelength conversion film 100 seals one surface of the wavelength conversion layer 102 with a conventional gas barrier film 104 and the other surface of the gas barrier film of the present invention ( It is sealed using the transfer layer 30 transferred from 10).

As described above, by sealing at least one surface of the wavelength conversion layer with the gas barrier film of the present invention, the entire thickness of the wavelength conversion film can be reduced.

In the example shown in Fig. 6, one side of the wavelength conversion layer is configured to be sealed with the gas barrier film of the present invention, but is not limited to this, and both surfaces of the wavelength conversion layer are sealed with the gas barrier film of the present invention. It may also be configured. Thereby, the thickness of the whole wavelength conversion film can be made thinner.

7 (A) to 7 (C) are examples of organic EL laminates in which the gas barrier film of the present invention is transferred to seal the organic EL element.

The organic EL stacked body 120a shown in FIG. 7A is transferred by laminating the element substrate 122, the organic EL element 124 formed on the element substrate 122, and the organic EL element 124. It has a layer 30.

As the element substrate 122, any element substrate used in various organic EL devices can be used. Specifically, an element substrate made of glass, plastic, metal, ceramic, or the like is exemplified. In addition, in order to prevent deterioration of the organic EL element 124 due to moisture or the like, it is preferable to prevent moisture or the like from passing through the element substrate 122 and reaching the organic EL element 124. For this reason, it is preferable to use a substrate made of a material having a low content such as moisture and a low transmittance such as moisture, such as glass or metal.

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

The organic EL element 124 is a known organic EL element having, for example, an organic electroluminescent layer and a transparent electrode and a reflective electrode that are electrode pairs that sandwich the organic electroluminescent layer.

As shown in the figure, the organic EL element 124 is sealed by the transfer layer 30 transferred from the gas barrier film 10 of the present invention.

Thus, by sealing the organic EL element 124 with the gas barrier film of the present invention, the thickness of the entire organic EL laminate can be reduced.

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

Further, as in the organic EL laminate 120c shown in Fig. 7C, 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 may be sealed with a passivation film 126, and a transfer layer 30 may be transferred onto the passivation film 126.

The passivation film 126 is for preventing moisture or oxygen from reaching the organic EL element 124 and deteriorating the organic EL element 124.

As the passivation film 126, various films (layers) made of a material that exhibits gas barrier properties, which are used in known organic EL devices, can be used. Specifically, a film made of an inorganic compound such as silicon nitride or silicon oxide having the same gas barrier properties as the inorganic layer 16 is exemplified.

The passivation film 126 may be formed by a known method according to the material for forming the film.

Hereinafter, the manufacturing method of the gas barrier film of this invention is demonstrated with reference to FIGS. 8 (A) and 8 (B).

In addition, the following example is a manufacturing method of a gas barrier film by R to R using the elongate board | substrate 12, the protective film 26, etc. as a preferable aspect. As is well known, R to R means that the object to be processed is transported from a roll formed by winding a long object to be processed, and the film is processed while being conveyed in the longitudinal direction, and the object to be processed is rolled again. It is a manufacturing method of winding in shape.

First, the release resin layer 20 is formed on the substrate 12 using the film forming apparatus conceptually shown in Fig. 8A.

Specifically, for example, a coating composition containing an organic solvent and an organic compound serving as the release resin layer 20 is prepared.

On the other hand, the substrate roll Ra formed by winding the long substrate 12 in a roll shape is loaded at a predetermined position in the organic film forming apparatus. Subsequently, the substrate 12 is sent out from the substrate roll Ra, and is notified to a predetermined path reaching the winding position. Further, the coating composition serving as the release resin layer 20 is filled in a predetermined position of the coating unit 40. The film forming apparatus has a pair of conveying rollers 48 for conveying the substrate 12 in a predetermined path.

Thereafter, the substrate 12 is sent out from the substrate roll Ra, and the prepared coating composition is applied to the substrate 12 in the coating unit 40 while conveying in the longitudinal direction, and then the coated coating composition is dried. The part 42 is dried and, if necessary, the cured part 44 is irradiated with ultraviolet rays or heated to form the release resin layer 20. Moreover, the long film with the release resin layer 20 formed on the board | substrate 12 is wound up in roll shape, and it is set as the base material roll Rb.

In addition, although illustration is omitted, as a preferable aspect, after forming the release resin layer 20, a protective film is laminated | stacked, and after that, it winds up and sets it as a base material roll Rb.

Next, the organic layer 14 is formed on the release resin layer 20 of the substrate to be formed as the substrate 12 on which the release resin layer 20 is formed as the substrate to be formed (Za). The formation of the organic layer 14 may basically be performed in the same manner as the formation of the release resin layer 20 using the organic film forming apparatus shown in Fig. 8A.

That is, for example, a coating composition comprising an organic solvent, an organic compound serving as the organic layer 14, and a polymerization initiator is prepared.

Moreover, the base material roll Rb formed by winding the long film-form base material Za into a roll shape is loaded in a predetermined position of the organic film-forming apparatus. Subsequently, the film-formed substrate Za is sent out from the substrate roll Rb, and a predetermined path reaching the winding position is notified. In addition, the coating composition serving as the organic layer 14 is filled in a predetermined position of the coating unit 40.

Thereafter, the film-formed substrate (Za) is delivered from the substrate roll (Rb), and the prepared coating composition is coated on the release resin layer (20) in the coating unit (40) while conveying in the longitudinal direction, and then applied One coating composition is dried in the drying unit 42, and the organic compound 14 is formed by polymerizing (crosslinking) the organic compound in the curing unit 44 by ultraviolet irradiation or the like. Moreover, the elongate film-form substrate Za which formed the organic layer 14 is wound in roll shape, and it is set as the base material roll Rc.

In addition, after formation of the organic layer 14, a protective film may be applied to the organic layer 14. It is preferable to adhere the protective film before the organic layer 14 contacts another member such as a guide roller.

Thereby, it is possible to prevent the organic layer 14, which is the underlying layer of the inorganic layer 16, from being damaged, and the inorganic layer 16 can be appropriately formed on the smooth organic layer 14, thereby providing high gas barrier properties. An expressing gas barrier film can be obtained.

Moreover, in the said example, although it was set as the structure which respectively forms the film of the peeling resin layer 20 and the film of the organic layer 14, it is not limited to this, After coiling the film of the peeling resin layer, after winding up, it continues, , The organic layer 14 may be formed. That is, in the conveyance path of the substrate 12, the coating part 40 for forming the release resin layer 20, the drying part 42 and the curing part 44, and the coating part for forming the organic layer 14 (40), a film forming apparatus in which a drying unit 42 and a curing unit 44 are disposed may be used to continuously form the release resin layer 20 and the organic layer 14.

Subsequently, in the inorganic film forming apparatus conceptually illustrated in Fig. 8B, the substrate 12 on which the release resin layer 20 and the organic layer 14 are formed (hereinafter referred to as "the film-forming substrate Zb") Is formed), and a protective film 26 is also attached to the inorganic layer 16 to produce a gas barrier film 10.

As an example, the inorganic film forming apparatus shown in FIG. 8 (B) forms an inorganic layer 16 by CCP-CVD (capacity-coupled plasma chemical vapor deposition method), and includes a supply chamber 50 and a film deposition chamber 52. And, it has a winding chamber (54).

First, the base roll Rc is loaded at a predetermined position in the supply chamber 50. Subsequently, the film-forming substrate Zb is sent out from the substrate roll Rc, and a predetermined path reaching the winding chamber 54 from the supply chamber 50 through the film-forming chamber 52 is notified. The base roll Rc is loaded so that the organic layer 14 becomes a film forming surface in the film forming chamber 52.

Further, the protective film roll 26R is loaded at a predetermined position in the film formation chamber 52. Subsequently, the protective film 26 is sent out from the protective film roll 26R, and a predetermined path from the film forming chamber 52 to the winding chamber 54 is notified.

Subsequently, the supply chamber 50 is evacuated by the vacuum evacuation means 50a, the film formation chamber 52 is evacuated by the vacuum evacuation means 52a, and the winding chamber 54 is evacuated by the vacuum evacuation means 54a, respectively. Each chamber is decompressed to a predetermined pressure.

When each seal reaches a predetermined pressure, the transfer of the film-forming base material Zb and the protective film 26 is started.

The film-forming substrate Zb is sent out from the substrate roll Rc, is guided to the guide roller 58, and is conveyed to the film-forming chamber 52.

The film-forming base material Zb conveyed to the film forming chamber 52 is guided to the guide roller 60 and is wound around the circumferential surface of the cylindrical drum 62. The drum 62 also serves as an electrode in CCP-CVD. Further, the drum 62 has a temperature control function as a preferred aspect. The film-formed substrate Zb is transported in a predetermined path by the drum 62, and the inorganic layer 16 is formed by CCP-CVD, and the release resin layer 20 and the organic layer are formed on the substrate 12. It becomes a laminated film in which the combination of (14) and the inorganic layer 16 was formed. CCP-CVD is a film forming means having an electrode pair comprising a drum 62 and a shower electrode 64, a raw material gas supply unit 68, a high frequency power supply 70, and the like.

The formation of the inorganic layer 16 by plasma CVD may be performed by a known method according to the material for forming the inorganic layer 16 or the like. In addition, in addition to CCP-CVD, various inorganic vapor deposition methods, such as ICP-CVD (inductively coupled plasma chemical vapor deposition method), sputtering, and vacuum vapor deposition, can be used to form the inorganic layer 16.

On the other hand, in synchronization with the conveyance of this film-forming substrate Zb, the protective film 26 is sent out from the protective film roll 26R, and is conveyed in the longitudinal direction.

The film-formed substrate Zb on which the inorganic layer 16 is formed and the protective film 26 are laminated and compressed by a lamination roller pair 72 to produce a gas barrier film 10.

In addition, an adhesive layer may be formed on the surface of the protective film 26 that faces the inorganic layer 16.

When producing the gas barrier film 10 by R to R, the protective film 26 is adhered, after the inorganic layer 16 is formed, before the inorganic layer 16 contacts other members such as a guide roller. It is desirable to do.

Thereby, the gas barrier film 10 which prevents damage of the inorganic layer 16 and expresses the target gas barrier property can be obtained.

The gas barrier film 10 produced by lamination and lamination of the laminated film and the protective film 26 by the laminated roller pair 72 is transferred from the film formation chamber 52 to the winding chamber 54, and the guide roller ( It is guided to a predetermined path by 76), and is wound up to become a gas barrier film roll Rd wound around the long gas barrier film 10.

In addition, when the film-forming base material Zb has a protective film on the organic layer 14, the protective film may be peeled off before the inorganic layer 16 is formed, and the inorganic layer 16 may be formed.

The peeling of the protective film is a path leading to the film forming means of the inorganic layer 16, and is preferably performed at a position where there is no member such as a guide roller contacting the organic layer 14.

In addition, when the organic protective layer 24 is further formed on the inorganic layer 16, avoid the substrate 12 on which the release resin layer 20, the organic layer 14, and the inorganic layer 16 are formed. As the film-forming base material, the organic film-forming apparatus shown in Fig. 8 (A) may be used to form the same as the release resin layer 20 and the organic layer 14.

As described above, the gas barrier film of the present invention has been described in detail, but the present invention is not limited to the above-described embodiments, and various improvements or changes may be made in a range not departing from the gist of the present invention. Of course.

Example

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

[Example 1]

As Example 1, a gas barrier film 10a shown in Fig. 1A was produced.

<Formation of the peeling resin layer 20>

As the substrate 12, a long PET film having a width of 1000 mm, a thickness of 50 µm, and a length of 100 m (Toyobo Co., Ltd., Cosmoshine A4100) was used.

The release resin layer 20 was formed in the following procedure on the unundercoat surface side of this substrate 12.

As the coating solution A1 serving as the release resin layer 20, a COC resin (APEL 6015T manufactured by Mitsui Chemical Co., Ltd.) was dissolved with cyclohexane to prepare a coating solution having a solid content concentration of 10%.

This coating liquid A1 was filled in the coating part 40 of the film forming apparatus by R to R shown in Fig. 8 (A). The coating part 40 used a die coater. Moreover, the substrate roll Ra formed by winding the substrate 12 in a roll shape was loaded at a predetermined position, and the substrate 12 was inserted into a predetermined conveyance path.

Subsequently, while conveying the substrate 12 in the longitudinal direction, the coating liquid A1 is applied to the substrate 12 by the coating unit 40 so that the dry film thickness is 2 μm, and in the drying unit 42, the drying temperature It dried at 100 degreeC for 3 minutes, and the release resin layer 20 was formed on the board | substrate 12. At this time, the hardened part 44 was not used.

That is, the material for forming the release resin layer 20 is a cycloolefin copolymer.

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

<Formation of organic layer 14>

Next, on the formed release resin layer 20, the organic layer 14 was formed in the following procedure.

As the coating solution B1 to be the organic layer 14, A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a photopolymerization initiator (BASF Japan, Irg819) were prepared and weighed to be 97: 3 as a weight ratio, and these were weighed. Dissolved in methyl ethyl ketone, a coating solution having a solid content concentration of 15% was prepared.

This coating liquid B1 was filled in the coating part 40 of the film forming apparatus by R to R shown in Fig. 8A. The coating part 40 used a die coater. Further, the substrate roll Rb formed by winding the substrate 12 having the release resin layer 20 (hereinafter sometimes referred to as a "film-forming substrate Za") in a roll shape is loaded at a predetermined position. , The film-formed substrate (Za) was inserted into a predetermined conveyance path.

Thereafter, the coating liquid B1 is applied onto the release resin layer 20 of the film-forming substrate Za by the coating unit 40 so that the dry film thickness is 1 μm while conveying the film-forming substrate Za in the longitudinal direction. Then, in the drying section 42, dried at a drying temperature of 50 ° C. for 3 minutes, and in the curing section 44, irradiated with ultraviolet rays (accumulated irradiation amount of about 700 mJ / cm ² ) to cure to release the resin layer 20 On this, an organic layer 14 was formed.

Moreover, after hardening the organic layer 14, a protective film of polyethylene was pasted onto the organic layer 14 before contacting the roll that first contacted the surface on the organic layer 14 side, and then wound up.

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

<Formation of inorganic layer 16>

Next, on the formed organic layer 14, the inorganic layer 16 was formed in the following procedure.

In the case where the release resin layer 20 and the organic layer 14 are formed on the substrate 12 at a predetermined position in the supply chamber 50 of the film forming apparatus shown in Fig. 8 (B) (hereinafter referred to as "film-forming substrate Zb") ), And the base material roll Rc formed by winding in a roll shape was loaded, and the protective film roll 26R was loaded at a predetermined position in the film formation chamber 52. Moreover, the film-formation base material Zb was sent out from the base material roll Rc, and the predetermined conveyance path which reached the winding-up chamber 54 from the supply chamber 50 through the film-forming chamber 52 was notified. Moreover, the protective film 26 was sent out from the protective film roll 26R, and the predetermined conveyance route which reached the winding chamber 54 from the film forming chamber 52 was notified.

In this state, the protective film is removed from the film-forming substrate Zb after passing through the film surface touch roll just before film-forming while synchronously conveying the film-forming substrate Zb and the protective film 26, and in the film-forming chamber 52 A silicon nitride film was formed as the inorganic layer 16 by CCP-CVD on the surface of the organic layer 14 of the film-forming substrate Zb supported / guided by the drum 62. Subsequently, the protective film 26 was laminated and adhered on the inorganic layer 16 by the lamination roller pair 72, and the gas barrier film 10a shown in FIG. 1 was produced and wound up.

For forming the inorganic layer 16, silane gas (flow rate of 160 sccm), ammonia gas (flow rate of 370 sccm), and hydrogen gas (flow rate of 2000 sccm) were used as the source gas. A high-frequency power source with a frequency of 13.56 MHz was used as the power source, and the plasma excitation power was 8 kW. The film-forming pressure was 40 Pa. The film thickness of the inorganic layer 16 was 30 nm.

After the inorganic layer 16 was formed, the protective film 26 was adhered before the inorganic layer 16 contacted another member. Moreover, a polyethylene film was used as the protective film 26.

[Example 2]

Moreover, the gas barrier film 10b 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.

As the coating liquid C1 which becomes the organic protective layer 24, a urethane skeleton acrylic polymer (Acryte 8BR930 manufactured by Daisei Fine Chemicals Co., Ltd.), a photopolymerization initiator (Irg184 manufactured by BASF Japan), a silane coupling agent (Shintsu Silicon KBM5103 manufactured by Kabuki Kaisha Co., Ltd., and a softener (byron U1400 manufactured by Toyobo Co., Ltd.) were weighed to 78: 10: 10: 2 as a weight ratio, dissolved in methyl ethyl ketone, and applied at a solid content of 15%. Was prepared.

This coating liquid C1 was filled in the coating part 40 of the film forming apparatus by R to R shown in Fig. 8 (A). The coating part 40 used a die coater. Further, the substrate roll formed by winding the substrate 12 (hereinafter sometimes referred to as "the film-formed substrate Zc") on which the release resin layer 20, the organic layer 14, and the inorganic layer 16 are formed is rolled. Was loaded at a predetermined position, and the film-formed substrate Zc was inserted into a predetermined conveyance path.

Subsequently, while conveying the film-formed substrate Zc in the longitudinal direction, the coating solution C1 was applied onto the inorganic layer 16 of the film-formed substrate Zc by the coating portion 40 so that the dry film thickness was 1 μm, and the drying portion ( (42), dried at a drying temperature of 100 ° C. for 3 minutes, and in the curing section 44, irradiated with ultraviolet rays (accumulated irradiation amount of about 600 mJ / cm ² ) to cure the organic protective layer on the inorganic layer 16 ( 24).

[Example 3]

As the coating liquid to be the organic protective layer 24, using the following coating liquid C2, the thickness of the organic protective layer 24 is 3 µm, and after forming the organic protective layer 24, the same as before, the first The gas barrier film 10c shown in Fig. 2 (B) is the same as in Example 2, except that a separator film (a film bar or BD manufactured by Fujimori High School) is applied as the protective film 26 as the second film surface touch roll. ).

The coating liquid C2 was diluted with butyl acetate in a ratio of 100: 2 by adding a curing agent L-45 (manufactured by Soken Chemical Co., Ltd.) to SK Dyne NT21 (manufactured by Soken Chemical Co., Ltd.) at a ratio of 100: 2, and the solid content concentration was 15. %.

This organic protective layer 24 is an acrylic adhesive.

[Example 4]

A gas barrier film 10c was produced in the same manner as in Example 3 except that a urethane-based adhesive (No. 96 manufactured by Rock Paint Co., Ltd.) was used as the coating liquid C3 to be the organic protective layer 24.

The organic protective layer 24 is a urethane-based adhesive.

[Example 5]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid A2 was used as the coating liquid to be the release resin layer 20.

The coating liquid A2 dissolved the COC resin (Mitsui Chemical Co., Ltd. APEL 6509T) with cyclohexane to prepare a solid content concentration of 10%.

The glass transition temperature Tg of the formed release resin layer 20 was measured in the same manner as before, 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.

The coating liquid A3 was prepared so that the COC resin (APEL 6011T manufactured by Mitsui Chemicals Co., Ltd.) 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 before, and was 105 ° C.

[Example 7]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid A4 was used as the coating liquid to be the release resin layer 20.

The coating liquid A4 was prepared such that the COP resin (Aton D4540 manufactured by JSR Corporation) was dissolved in cyclohexane to obtain a solid content concentration of 10%.

The glass transition temperature Tg of the formed release resin layer 20 was measured in the same manner as before, and was 128 ° C.

[Example 8]

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

[Example 9]

The gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and coating amount of the coating solution A1 serving as the release resin layer 20 were changed and the dry film thickness was set to 10 μm.

[Example 10]

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

[Example 11]

The gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and coating amount of the coating solution A1 serving as the release resin layer 20 were changed and the dry film thickness was set to 0.1 μm.

[Example 12]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B2 was used as the coating liquid to be the organic layer 14.

The coating solution B2 was formulated so that 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.) became 4: 1. , This and the photopolymerization initiator (BASF Japan Irg819) were weighed to 97: 3 by weight ratio, dissolved in methyl ethyl ketone, and prepared at a solid content concentration of 15%.

When the glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as before, it was 180 ° C.

[Example 13]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B3 was used as the coating liquid to be the organic layer 14.

The coating liquid B3 was formulated such that 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.) became 1: 1. , This and the photopolymerization initiator (BASF Japan Irg819) were weighed to 97: 3 by weight ratio, dissolved in methyl ethyl ketone, and prepared at a solid content concentration of 15%.

When the glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as before, it was 114 ° C.

[Example 14]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B4 was used as the coating liquid to be the organic layer 14.

The coating solution B4 was weighed so as to make 97: 3 by weight ratio of EB3702 (Tg 53 ° C) manufactured by Daicel Allnex Co., Ltd. and photopolymerization initiator (BASF Japan Irg819), dissolved in methyl ethyl ketone, and solid content. It was prepared at a concentration of 15%.

When the glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as before, it was 53 ° C.

[Example 15]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B5 was used as the coating liquid to be the organic layer 14.

The coating liquid B5 is A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1-ADMA (1-adamantyl methacrylate Osaka Yuki Chemical Co., Ltd. Tg 250 ° C). It was formulated to be 1: 1, and this and a photopolymerization initiator (BASF Japan Irg819) were weighed to 97: 3 by weight, dissolved in methyl ethyl ketone, and prepared at a solid content concentration of 15%.

That is, the material for forming the organic layer contains one or more acrylates having an adamantane skeleton.

The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as before, and was 250 ° C.

[Example 16]

A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating liquid B6 was used as the coating liquid to be the organic layer 14.

The coating liquid B6 was formulated such that A-DPH (Tg 250 ° C or higher manufactured by Shin-Nakamura Chemical Co., Ltd.) and EA-200 (Tg 211 ° C manufactured by acrylate monomer Osaka Gas Chemical Co., Ltd.) became 1: 1. , This and the photopolymerization initiator (BASF Japan Irg819) were weighed to 97: 3 by weight ratio, dissolved in methyl ethyl ketone, and prepared at a solid content concentration of 15%.

That is, the material for forming the organic layer contains a bifunctional or higher acrylate having a fluorene skeleton.

The glass transition temperature Tg of the formed organic layer 14 was measured in the same manner as before, and was 230 ° C.

[Example 17]

As the inorganic layer 16, a gas barrier film 10a was produced in the same manner as in Example 1 except that an aluminum oxide film (alumina film) was formed.

The aluminum oxide film was formed by a general sputtering device. Specifically, an inorganic layer 16 made of an aluminum oxide film was formed by DC magnetron sputtering using an alumina sintered compact as a target.

[Example 18]

The gas barrier film 10a was produced in the same manner as in Example 1 except that the solid content concentration and coating amount of the coating liquid B1 serving as the organic layer 14 were changed, and the dry film thickness was 5 μm.

[Example 19]

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

[Example 20]

A gas barrier film 10a was produced in the same manner as in Example 1 except that a silicon release film (film bar or BD manufactured by Fujimori High School Co., Ltd.) was used as the substrate 12.

[Example 21]

The gas barrier film 10c was produced in the same manner as in Example 3, except that the solid content concentration and coating amount of the coating liquid C2 serving as the organic protective layer 24 were changed and the dry film thickness was set to 50 μm.

[Example 22]

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

[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 forming the release resin layer 20, after drying, ultraviolet rays were irradiated with a cumulative irradiation amount of about 3000 mJ / cm ² , and then cured and wound. Next, the cumulative irradiation amount of ultraviolet rays when forming the organic layer 14 was changed to about 50 mJ / cm ² . A gas barrier film was produced in the same manner as in Example 1 except for these.

Thereby, the peeling force between the organic layer 14 and the peeling resin layer 20 was weakened while strengthening the peeling force between the peeling resin layer 20 and the substrate 12. Thereby, the peeling force of the organic layer 14 and the peeling resin layer 20 was made weaker than the peeling force of the peeling resin layer 20 and the substrate 12. That is, it was made to peel between the peeling resin layer 20 and the organic layer 14.

[evaluation]

The gas barrier films and optical properties of the produced gas barrier films of Examples 1 to 22 and Comparative Examples 1 and 2 were evaluated.

<Gas barrier property>

(Transfer process)

As an object to be transferred, a TAC film of 200 mm square, in which an adhesive layer was bonded to a Fuji Tak (manufactured by TD80 Fuji Film Co., Ltd.) with an optical adhesive film (manufactured by PDS1 Panak Corporation) was prepared.

After peeling off the protective film 26 of the produced gas barrier film 10, by a laminator (proteus manufactured by Fellows), the adhesive layer of the object to be transferred and the inorganic layer 16 of the gas barrier film 10 come into contact with each other. I put it together. Thereby, a 200 mm square bonding film was obtained. The lamination pressure was 0.5 MPa, and the conveying speed was 5 m / min.

After bonding, the substrate 12 of the gas barrier film 10 was peeled off. The substrate 12 was peeled as follows. First, a 200 mm square bonded film was punched to 100 mm square using a Thompson blade so that the end faces were peeled off clearly. Subsequently, after the TAC film side was turned down and the TAC film surface was adsorbed and held by a highly planar adsorption plate, an adhesive tape (Nitto Cellotape (registered trademark)) for holding the substrate 12 was attached to the end portion of about 2 cm. . Subsequently, the adhesive tape was pulled parallel to the sample so that the substrate 12 arced like the 180 degree peel test. In this way, the substrate 12 was peeled off. At the time of peeling, it was performed in an environment at a temperature of 25 ° C and a humidity of 50% RH.

In addition, with respect to Examples 3, 4, 21, and 22, which have an organic protective layer 24 serving as an adhesive layer on the inorganic layer 16, Fuji Tak (TD80 Fujifilm Co., Ltd.) does not adhere the adhesive film. The transfer was carried out in the same manner as in Example 1, except that () was a transfer object.

(Measurement of water vapor transmission rate)

The water vapor transmission rate of the gas barrier film 10 transferred to an object to be transferred and peeling off the substrate 12 was measured by a calcium corrosion method (method described in JP 2005-283561 A). The conditions of the constant temperature and constant humidity treatment were set to a temperature of 40 ° C and a relative humidity of 90% RH.

Moreover, the water vapor transmittance of Fujitak simple substance was 400 [g / (m ² · day)].

Based on the measured water vapor transmission rate, evaluation was made based on the following criteria.

A: Water vapor transmittance is less than 5 × 10 ^-5 [g / (m ² · day)]

B: The 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 of 1 × 10 ^-4 or more and less than 5 × 10 ^-4 [g / (m ² · day)]

D: Water vapor transmittance is 5 × 10 ^-4 or more and less than 1 × 10 ^-3 [g / (m ² · day)]

E: Water vapor transmission rate of 1 × 10 ^-3 [g / (m ² · day)] or more

<Optical characteristics>

After peeling off the protective film 26 of the produced gas barrier film 10, the substrate 12 is peeled off, and the release resin layer 20 and the gas barrier layer 18 (organic layer 14 and inorganic layer 16) )) Was taken out. Subsequently, the total light transmittance and retardation value of the transfer layer 30 were measured.

(Total light transmittance)

The total light transmittance of the taken-out transfer layer 30 was measured using a spectrophotometer (Hazemeter SH7000 manufactured by Nippon Denshoku Co., Ltd.).

It evaluated based on the following criteria based on the measured total light transmittance.

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%

(Retardation value)

The retardation value (Re value) of the taken-out transfer layer 30 was measured by KOBRA-WR (Oji Scientific Instruments, Ltd.).

It evaluated based on the following criteria based on the measured retardation value.

A: Retardation value is 5 nm or less

B: The retardation value is more than 5 nm and less than 10 nm

C: Retardation value is more than 10nm and less than 20nm

D: Retardation value exceeds 20 nm

The results are shown in the table below.

[Table 1]

As shown in Table 1, the embodiment of the present invention having a release resin layer between the substrate and the gas barrier layer, and peeling at the interface between the release resin layer and the substrate, compared with the comparative example, gas barrier properties and optical It can be seen that the properties are excellent.

Moreover, from the contrast of Examples 1, 5, and 6, it turns out that it is preferable that the release resin layer is a cyclic olefin resin whose glass transition temperature Tg is 100 degreeC or more.

Moreover, it turns out that it is preferable that a peeling resin layer is a cycloolefin copolymer from the contrast of Example 1 and Example 7.

Moreover, from the contrast of Examples 1 and 8-11, it turns out that 0.1-25 micrometers is preferable and 0.5-15 micrometers of thickness of a peeling resin layer is more preferable.

Moreover, it can be seen from the contrast of Examples 1 and 12 to 14 that the glass transition temperature Tg of the organic layer is preferably 200 ° C or higher.

Moreover, from the contrast of Examples 1, 15 and 16, the organic layer preferably contains 5% by weight or more and less than 50% by weight of a monofunctional or higher acrylate having an adamantane skeleton, or has a fluorene skeleton It can be seen that it is preferable to contain at least 5% by weight and less than 50% by weight of the bifunctional or higher acrylate.

Further, from the contrast of Examples 1, 18 and 19, it can be seen that the thickness of the organic layer is preferably 0.1 to 50 μm, more preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm.

In addition, it can be seen from the contrast between Examples 1 and 17 that the inorganic layer is preferably silicon nitride.

Moreover, it turns out that it is preferable to have the organic protective layer 24 on the inorganic layer 16 from Examples 2-4, 21, and 22.

Moreover, it can be seen from the contrast between Examples 3 and 4 that it is preferable to use an acrylic pressure-sensitive adhesive as the organic protective layer 24.

Moreover, it can be seen from the contrast of Examples 3, 21, and 22 that the thickness of the organic protective layer 24 is preferably 0.1 to 50 μm, and more preferably 0.5 to 25 μm.

[Example 23]

The wavelength conversion film 100 shown in FIG. 6 was produced using the produced gas barrier film 10. The wavelength conversion film was 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 filter made of polypropylene having a pore diameter of 0.2 µm, dried under reduced pressure for 30 minutes, and used as a coating composition. The quantum dot concentration in the following toluene dispersion was 1% by mass.

(Polymer dot-containing polymerizable composition A)

Toluene dispersion of quantum dot 1 (maximum emission: 520 nm) 10.0 parts by mass

1.0 part by mass of quantum dot 2 toluene dispersion (luminescence maximum: 630 nm)

・ 80.8 parts by weight of lauryl methacrylate

Trimethylolpropane triacrylate 18.2 parts by mass

1.0 part by weight of photopolymerization initiator

(Irgacure 819 (manufactured by BASF))

<Production of quantum dot film>

As two films (first film and second film), the gas barrier film 10a of Example 1 was prepared. That is, the thing of the same structure was used as a 1st film and a 2nd film.

First, while continuously conveying the first film at a tension of 1 m / min and 60 N / m, the protective film 26 on the inorganic layer 16 is peeled off, and on the inorganic layer 16, the coating composition prepared above is prepared. It was applied with a die coater to form a 50 μm thick coating film.

Subsequently, the film on which the coating film was formed was wound on a backup roller. The protective film 26 was peeled from the second film, and the inorganic layer 16 was laminated in the direction in contact with the coating film. In this way, the coating film was pinched by the first film and the second film.

While continuously conveying in this state, the heating zone at 60 ° C. was passed for 3 minutes, and then irradiated with ultraviolet rays and cured using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to contain quantum dots. A quantum dot layer (wavelength conversion layer 102) was formed. In addition, the irradiation amount of ultraviolet rays was 2000 mJ / cm ² .

The substrate 12 was peeled from each of the first film and the second film to produce a quantum dot film (wavelength conversion film 100).

[evaluation]

The wavelength conversion film 100 of Example 23 produced was evaluated for durability.

Specifically, the luminance of the wavelength conversion film 100 immediately after production, and the luminance after being left for 1000 hours in an environment at a temperature of 60 ° C. and a humidity of 90% RH (after humidification) were measured, and durability was evaluated from the amount of change. .

The luminance was measured as follows.

First, a commercially available liquid crystal display device (Kindle Fire HDX 7 "manufactured by Amazon) was disassembled to take out a backlight unit having a blue light source. Next, a wavelength converting film cut into a rectangle was placed on the light guide plate of the backlight unit, and On the above, two prism sheets taken out from the liquid crystal display device were superimposed and arranged so that the direction of the uneven pattern on the surface was orthogonal.

The backlight unit was turned on, and the luminance was measured with a luminance meter (SR3 manufactured by TOPCON) installed at a position of 740 mm in the vertical direction from the front side of the backlight unit.

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

[Example 24]

The retardation film 110 with a gas barrier layer shown in FIG. 5 was produced using the produced gas barrier film 10.

As the retardation film 112, special polycarbonate W138 (made by Teijin Co., Ltd.) was used.

First, an optical adhesive film (manufactured by PDS1 Panak Co., Ltd.) was pasted onto the retardation film 112.

Next, after peeling off the protective film 26 of the gas barrier film 10a of Example 1, the adhesive layer side of the retardation film 112 and the inorganic layer 16 of the gas barrier film 10 are in contact, Bonding was carried out by a laminator (Proteus manufactured by Peroz Corporation). After bonding, the substrate 12 of the gas barrier film 10 was peeled to produce a phase difference film 110 with a gas barrier layer.

[evaluation]

The optical property of the retardation film 110 with a gas barrier layer of Example 24 was evaluated.

Specifically, when the retardation values of the retardation film 112 alone and the retardation film 110 with the gas barrier layer were measured, the difference was 2% or less. Therefore, it can be seen that the retardation film 110 with the gas barrier layer transferred with the gas barrier film of the present invention has high gas barrier properties while maintaining optical properties.

[Example 25]

Using the produced gas barrier film 10, an organic EL laminate 120a shown in Fig. 7A was produced.

<Production of organic EL elements>

A glass plate having a thickness of 500 μm and a size of 20 × 20 mm was prepared as the element substrate 122.

The peripheral 2 mm of the element substrate 122 was masked with ceramic. Further, the masked device substrate was loaded in a general 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. Subsequently, the following organic compound layers were sequentially formed on the device substrate 122 by vacuum deposition.

((Emission layer and electron transport layer) Tris (8-hydroxyquinolinate) aluminum: film thickness 60 nm

((Second hole transport layer)) N, N'-diphenyl-N, N'-dynaphthylbenzidine: film thickness 40 nm

((1st hole transport layer) copper phthalocyanine: film thickness 10 nm

In addition, the element substrate 122 having these layers was loaded into a general sputtering apparatus, and used as a target for ITO (Indium Tin Oxide Indium Tin Oxide), and by DC magnetron sputtering, into an ITO thin film having a thickness of 0.2 μm. A transparent electrode was formed. In this way, on the element substrate 122, an organic EL element 124, which is a light emitting element using an organic EL material, was formed.

<Transfer of gas barrier film>

Subsequently, masking was removed from the element substrate 122 on which the organic EL element 124 was formed. An acrylic adhesive was applied to the element substrate 122 with the masking removed. Next, the protective film 26 is peeled off from the gas barrier film 10a of Example 1, the gas barrier film 10a is pasted with the inorganic layer 16 facing the adhesive surface, and thereafter, the gas barrier The substrate of the film 10a was peeled to produce an organic EL laminate 120a.

[Example 26]

After removing the masking, the element substrate 122 on which the organic EL element 124 is formed is loaded in a general plasma CVD apparatus, and the passivation film 126 made of silicon nitride, made of silicon nitride by plasma CVD (CCP-CVD), is formed. An organic EL laminate 120c shown in Fig. 7C was produced in the same manner as in Example 25, except for forming.

[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 Example 1 is attached to a TAC film in which an adhesive layer is pasted, in which an optical adhesive film (manufactured by PDS1 Panak Co., Ltd.) is attached to Fuji Tak (manufactured by TD80 Fuji Film). Was transferred, and a laminate obtained by peeling off the substrate 12 was used as the element substrate 122. Then, the organic EL element 124 was formed on the release resin layer 20 of the element substrate 122.

Subsequently, the organic EL element 124 was sealed with another one gas barrier film 10a in the same manner as the above to produce an organic EL laminate 124.

[evaluation]

The organic EL laminates of Examples 25 to 27 produced were evaluated for durability.

Specifically, the produced organic EL laminate 124 was left in an environment at a temperature of 60 ° C. and a humidity of 90% RH for 200 hours. After standing, each organic EL laminate 124 was lighted by applying a voltage of 7 V using a SMU2400 type source measure unit manufactured by Keithlel. It observed with the microscope from the gas barrier film (10a side) side, the presence or absence of dark spot generation was confirmed, and it evaluated by the following criteria.

A: Dark spots were not observed at all.

B: Dark spots were slightly observed.

C: The occurrence of dark spots was clearly confirmed

D: The proportion of the dark spot area is large

As a result of the evaluation, all of the organic EL laminates of Examples 25 to 27 were A.

From the above results, the effect of the present invention is clear.

10 gas barrier film
12 substrate
14 organic layer
16 inorganic layers
18 gas barrier layer
20 release resin layer
24 organic protective layer
26 protective film
30 Warrior Layer
40 applicator
42 Drying section
44 Hardened part
48 transfer roller pairs
50 supply rooms
50a, 52a, 54a vacuum exhaust means
52 Tabernacle
54 winding room
58, 60, 76 guide rollers
62 drums
64 shower electrodes
68 Raw material gas supply
70 high frequency power
72 lamination roller pair
100 wavelength conversion film
102 wavelength conversion layer
104 gas barrier film
110 gas barrier layer retardation film
112 retardation film
120 organic EL laminate
122 element substrate
124 organic EL devices
126 passivation membrane

Claims (24)

Substrate,
A gas barrier layer provided on one side of the substrate and having at least one set of a combination of an inorganic layer and an organic layer serving as a formation surface of the inorganic layer,
It is provided between the substrate and the gas barrier layer, is in close contact with the organic layer, and further has a release resin layer for peeling the substrate and the gas barrier layer,
The organic layer is thinner than the release resin layer, and the glass transition temperature of the organic layer is higher than the glass transition temperature of the release resin layer,
The material for forming the release resin layer is a cycloolefin copolymer,
The material for forming the organic layer is an ultraviolet curing resin or an electron beam curing resin, and the glass transition temperature Tg after curing is 200 ° C. or higher,
The material for forming the organic layer contains at least 5% by weight, less than 50% by weight of at least one acrylate having an adamantane skeleton, or at least 5% by weight, at least 50% by weight of acrylates having a fluorene skeleton. A gas barrier film comprising less than. The method according to claim 1,
The gas barrier film in which the material for forming the release resin layer is a cyclic olefin resin having a glass transition temperature Tg of 100 ° C or higher. The method according to claim 1,
The gas barrier film whose thickness of the said peeling resin layer is 0.1-25 micrometers. The method according to claim 1,
The gas barrier film, wherein the material for forming the inorganic layer is silicon nitride, silicon oxide, or a mixture thereof. The method according to claim 1,
A gas barrier film having a thickness of the organic layer of 0.1 to 5 μm. The method according to claim 1,
A gas barrier film further provided on the gas barrier layer, further comprising a protective film or an organic protective layer. The method according to claim 6,
The gas barrier film, wherein the organic protective layer is an acrylic adhesive. The method according to claim 6,
A gas barrier film further comprising a protective film provided on the organic protective layer. The method according to claim 6,
A gas barrier film having a thickness of the organic protective layer of 0.1 to 50 μm. The method according to claim 1,
A gas barrier film, wherein the substrate is a polyethylene terephthalate film provided with a release layer. The method according to claim 1,
A gas barrier film having a water vapor transmission rate of less than 0.01 g / (m ² · day) in a configuration in which the substrate is removed. The method according to claim 1,
A gas barrier film having a visible light transmittance of 85% or more and a retardation value of 30 nm or less in a configuration in which the substrate is removed. As a transfer method of a gas barrier film for transferring a transfer layer comprising a gas barrier layer and a release resin layer to an image transfer body,
The surface of the gas barrier film according to claim 1, which is opposite to the substrate, is adhered to the transfer body,
A method of transferring a gas barrier film, wherein the substrate is peeled off. The method according to claim 13,
The method for transferring a gas barrier film, 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 layer,
The wavelength conversion film which has the transfer layer provided with the said gas barrier layer and the said peeling resin layer which removed the said board | substrate from the gas barrier film of Claim 1 laminated | stacked on the said wavelength conversion layer. Retardation film,
The phase difference film with a gas barrier layer which has the transfer layer provided with the said gas barrier layer and the said peeling resin layer which removed the said board | substrate from the gas barrier film of Claim 1 laminated | stacked on the said phase difference film. An organic EL element,
An organic EL laminate having a transfer layer comprising the gas barrier layer and the release resin layer, the substrate being removed from the gas barrier film according to claim 1 laminated on the organic EL element. The method according to claim 17,
An organic EL laminate having a passivation film between the organic EL element and the transfer layer. The method according to claim 17,
Further having a device substrate for supporting the organic EL device,
The element substrate includes the transfer layer including the gas barrier layer and the release resin layer, from which the substrate is removed from the gas barrier film, and an organic EL laminate. delete delete delete delete delete

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