JP6527053B2 - Gas barrier film and transfer method of gas barrier film - Google Patents

Description

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

In recent years, high gas barrier properties are required in devices such as organic EL devices (organic electroluminescent devices), solar cells, quantum dot films, and display materials, and in packaging materials such as infusion bags containing chemicals that deteriorate due to moisture or oxygen. .
Therefore, necessary gas barrier properties are imparted to these members by sticking a gas barrier film or sealing with a gas barrier film.

  In order to use such a gas barrier film in a field where high gas barrier properties are required, Patent Document 1 discloses, as a method of improving the gas barrier properties, a configuration using an inorganic layer as a gas barrier layer or a configuration in which the gas barrier layer is multilayered. It is described that a gas barrier layer is formed on a resin film having a high glass transition temperature Tg.

A barrier film having such high gas barrier properties is developed into various electronic devices and functional films, and it is possible to seal materials that were conventionally difficult to seal.
For example, Patent Document 2 protects quantum dots by sandwiching a quantum dot layer (QD phosphor material film layer) with two gas barrier films as a quantum dot film used for a backlight unit such as LCD. Stacked quantum dot films have been described.
Moreover, patent document 3 describes sealing an organic EL element using a gas barrier film.

By using a gas barrier film having high gas barrier properties as described above, thinning, weight reduction, and flexibility of various electronic devices such as a display can be performed. Therefore, if the gas barrier film can be further thinned, the thickness and weight of the electronic device can be further reduced.
As described in Patent Document 1 and the like, such a gas barrier film has a configuration in which a gas barrier layer is formed on a resin film as a substrate. Therefore, in order to reduce the thickness of the gas barrier film, it is conceivable to reduce the thickness of the substrate.
Here, the gas barrier layer having high gas barrier properties is a thin inorganic layer, which is broken by minute buckling or contact, and the performance is degraded. Therefore, when laminating the gas barrier layer on a thin substrate, it is necessary to stabilize transport so as to prevent the substrate from buckling.

Therefore, in Patent Document 4, the self-supporting property of the substrate can be secured by sticking the protective material on the back side of the substrate, and even when a thin substrate is used, buckling of the substrate does not occur. It is described that the gas barrier layer can be properly formed.
By using such a method, it is possible to form a gas barrier layer even on a thin substrate of about 10 μm or so. However, if the thickness is smaller than this range, it becomes difficult to bond a protective material for reinforcement while transporting a thin substrate.

  As a method of solving the problem accompanying thinning of such a gas barrier film, the transfer system which transcribes | transfers only a gas barrier layer to a sealing target object (transferred object) is proposed.

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

U.S. Pat. No. 5,654,084 Japanese Patent Publication No. 2013-544018 gazette JP, 2014-197537, A JP, 2015-66812, A Unexamined-Japanese-Patent No. 2007-118564

As described above, in order to achieve high gas barrier properties, the gas barrier layer needs to have an inorganic layer.
Here, according to the study of the present inventor, in the case of a transfer type gas barrier film in which the gas barrier layer is peeled off from the substrate and transferred to the transfer target as described in Patent Document 5, the gas barrier layer and the substrate are peeled off. Since shear force is applied to the gas barrier layer when carrying out, it was found that the inorganic layer may be broken by this shear force and the gas barrier layer after transfer may not exhibit sufficient gas barrier properties.

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

As a result of intensive studies to achieve the above problems, the present inventor has found that the substrate and the gas barrier layer provided on one surface of the substrate have at least one combination of an inorganic layer and an organic layer to be the formation surface of the inorganic layer. Further, it has been found that the above problems can be solved by providing a peeling resin layer provided between the substrate and the gas barrier layer, in close contact with the organic layer, and for peeling off the substrate, and the present invention has been completed. .
That is, the present invention provides a gas barrier film having the following constitution and a method for producing the gas barrier film, and a wavelength conversion film, a retardation film with a gas barrier layer, and an organic EL laminate using the gas barrier film.

(1) substrate,
A gas barrier layer having at least one combination of an inorganic layer and an organic layer to be a formation surface of the inorganic layer provided on one surface of a substrate;
A gas barrier film provided between a substrate and a gas barrier layer, in close contact with an organic layer, and a peeling resin layer for peeling the substrate.
(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 peeling 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), wherein 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 thickness of the release resin layer is 0.1 to 25 μm.
(6) The gas barrier film according to any one of (1) to (5), wherein the forming material of 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 forming material of 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.
(8) The gas barrier film according to (7), wherein the material for forming the organic layer contains 5% or more and less than 50% of a monofunctional or higher functional acrylate having an adamantane skeleton.
(9) The gas barrier film according to (7), wherein the material for forming the organic layer contains 5% or more and less than 50% of a bifunctional or higher functional 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), having a protective film or an organic protective layer 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), which has a protective film 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 according to any one of (1) to (15), wherein the water vapor transmission rate of the transfer layer comprising the gas barrier layer and the release resin layer from which the substrate has been peeled is less than 0.01 g / (m ² · day). the film.
(17) The gas barrier film according to any one of (1) to (16), wherein the visible light transmittance of the transfer layer comprising the gas barrier layer and the release resin layer is 85% or more and the retardation value is 30 nm or less. .
(18) A surface on the opposite side to the substrate of the gas barrier film according to any one of (1) to (17) is attached to a substrate to be transferred, and the substrate is peeled to provide a gas barrier layer and a peeling resin layer. The transfer method of the gas barrier film which transcribes | transfers a transfer layer to a to-be-transferred body.
(19) The method for transferring a gas barrier film according to (18), wherein the transfer target is any 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,
The wavelength conversion film which has a transfer layer provided with the gas barrier layer and the peeling resin layer which peeled the board | substrate from the gas barrier film in any one of (1)-(17) laminated | stacked on the wavelength conversion layer.
(21) Retardation film,
A gas barrier layer provided retardation film having a gas barrier layer and a transfer layer comprising a release resin layer, wherein the substrate is peeled off from the gas barrier film according to any one of (1) to (17), laminated on the retardation film.
(22) Organic EL elements,
The organic EL laminated body which has a transfer layer provided with the gas barrier layer and the peeling resin layer which peeled the board | substrate from the gas barrier film in any one of (1)-(17) laminated | stacked on organic EL.
(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 for supporting an organic EL device, comprising a transfer layer comprising a gas barrier layer and a release resin layer, wherein the substrate is released from the gas barrier film according to any one of (1) to (17) The organic electroluminescent laminated body as described in (23).

  According to the present invention, a gas barrier film which is thin, transferable, and has high gas barrier properties even after transfer, and a method of manufacturing the gas barrier film, and a wavelength conversion film using the gas barrier film It is possible to provide a retardation film and an organic EL laminate.

FIG. 1 (A) is a diagram conceptually showing an example of the gas barrier film of the present invention, and FIG. 1 (B) is a diagram conceptually showing a state in which the substrate is peeled from the gas barrier film of FIG. It is. FIGS. 2 (A) and 2 (B) are views conceptually showing another example of the gas barrier film of the present invention. It is a figure which shows notionally another example of the gas barrier film of this invention. FIG. 4A to FIG. 4C are conceptual diagrams for explaining the transfer method of the gas barrier film of the present invention. It is a figure which shows notionally an example of the retardation film with a gas barrier layer of this invention. It is a figure which shows notionally an example of the wavelength conversion film of this invention. FIGS. 7A to 7C are views conceptually showing an example of the organic EL laminate of the present invention. FIG. 8 (A) and FIG. 8 (B) are figures which show notionally an example of the film-forming apparatus which manufactures the gas barrier film of this invention.

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

  The gas barrier film of the present invention comprises a substrate, a gas barrier layer provided on one surface of the substrate, at least one combination of an inorganic layer and an organic layer to be a surface on which the inorganic layer is formed, and the substrate and the gas barrier layer It is a gas barrier film provided and closely_contact | adhered with the organic layer, and having a peeling resin layer for peeling with a board | substrate. The 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 a transfer target.

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

Here, as shown in FIG. 1 (B), in the gas barrier film 10a, the peeling resin layer 20 is in close contact with the organic layer 14 and is configured to be peelable from the substrate 12 at the interface with the substrate 12. That is, the peeling force (adhesion force) between the organic layer 14 and the peeling resin layer 20 is larger than the peeling force between the substrate 12 and the peeling resin layer 20.
Thereby, the gas barrier film 10a can peel only the board | substrate 12, and can transcribe | transfer the transfer layer 30 containing the gas barrier layer 18 and the peeling resin layer 20 to the to-be-transcribed body which is a sealing target object.
The transfer of the transfer layer 30 to the transfer target basically involves bonding the gas barrier layer 18 side of the gas barrier film 10a to the transfer target, and then peeling off the substrate 12 from the gas barrier film 10a to form the transfer layer 30. The transfer layer 30 may be bonded to the transfer target after the substrate 12 is peeled off from the gas barrier film 10 a and the transfer layer 30 is taken out.

As described above, as a thinner gas barrier film, a transfer type gas barrier film has been proposed in which a release layer is formed between a substrate and a gas barrier layer, and the gas barrier layer is peeled from the substrate and transferred to a transfer target. .
However, according to the study of the present inventor, in such a transfer type gas barrier film, when peeling the gas barrier layer and the substrate, a shearing force is applied to the gas barrier layer, and the inorganic layer is broken by this shearing force. As a result, it has been found that the gas barrier layer after transfer sometimes can not exhibit sufficient gas barrier properties.

On the other hand, in the present invention, an organic layer 14 is provided as a base of the inorganic layer 16 exhibiting gas barrier properties, and a peeling resin layer 20 is provided between the organic layer 14 and the substrate 12. The peeling resin layer 20 is in close contact with the organic layer 14 and is configured to be peelable from the substrate 12 at the interface with the substrate 12.
By peeling at the interface between the peeling resin layer 20 and the substrate 12 at the time of peeling, the peeling resin layer 20 present between the inorganic layer 16 and the peeling surface becomes a stress relaxation layer, and when peeling the substrate 12 The shear force can prevent the inorganic layer 16 from being broken.

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. Therefore, 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 to be the base of the inorganic layer 16 needs to have appropriate hardness and higher heat resistance.
Therefore, 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 formed directly on the release resin layer 20, the inorganic layer 16 is appropriate. Can not be formed, and high gas barrier properties can not be obtained.

  On the other hand, in the present invention, since the organic layer 14 is provided on the release resin layer 20 as a base layer of the inorganic layer 16, a suitable base layer can be formed. Therefore, the inorganic layer 16 can be appropriately formed, and high gas barrier properties can be obtained.

Further, the gas barrier film of the present invention preferably further has a protective film for protecting the gas barrier layer 18 (inorganic layer 16) on the gas barrier layer 18.
By having a protective film, it is possible to prevent the inorganic layer 16 from being broken during transportation or winding of the gas barrier film.
In the case where the gas barrier film has a protective film, the protective film may be peeled off to expose the gas barrier layer 18, and then transfer to a transfer target may be performed.

Moreover, it is also preferable to have the organic protective layer 24 for protecting the gas barrier layer 18 on the gas barrier layer 18 (inorganic layer 16) like the gas barrier film 10b shown to FIG. 2 (A).
By having the organic protective layer 24, it is possible to prevent the inorganic layer 16 from being broken when transporting the gas barrier film or when winding it up.
When the organic protective layer 24 is provided, the peeling 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 becomes the transfer target together with the peeling resin layer 20 and the gas barrier layer 18. Transcribed.

Moreover, the organic protective layer 24 may be an adhesive layer having adhesiveness.
When the organic protective layer 24 has adhesiveness, when the transfer layer 30 is transferred to a transfer-receiving material, transfer can be easily performed without applying an adhesive or the like.

Further, as in a gas barrier film 10c shown in FIG. 2B, the organic protective layer 24 may be provided on the gas barrier layer 18, and the protective film 26 may be further provided on the organic protective layer 24.
By having the organic protective layer 24 and the protective film 26, it is possible to prevent the inorganic layer 16 from being broken when transporting the gas barrier film or when winding it up.
When the organic protective layer 24 is an adhesive layer, the protective film 26 can facilitate transport and winding of the gas barrier film, and dust or the like may adhere to the adhesive layer. It is possible to prevent the adhesion from decreasing.

Further, in the example shown in FIG. 1A, the gas barrier layer 18 is configured to have one organic layer 14 and one inorganic layer 16, but this is not a limitation, and the organic layer and the inorganic layer are not limited. And the organic layer 14 to be the base layer of the inorganic layer 16 and the inorganic layer 16 may have two or more sets.
For example, the gas barrier film 10d shown in FIG. 3 has the gas barrier layer 18 in which the organic layer 14, the inorganic layer 16, the organic layer 14 and the inorganic layer 16 are formed in this order on the release resin layer 20. That is, the gas barrier layer 18 of the gas barrier film 10 d is configured to have two combinations of the organic layer 14 and the inorganic layer 16.
Thus, gas barrier property can be further improved by having two or more sets of combinations of the organic layer 14 and the inorganic layer 16.

Here, in the gas barrier film of the present invention, the water vapor transmission rate of the transfer layer 30 provided with the gas barrier layer 18 and the release resin layer 20 from which the substrate 12 has been removed is less than 0.01 [g / (m ² · day)]. It is preferably present, more preferably 0.005 [g / (m ² · day)] or less, and particularly preferably 0.001 [g / (m ² · day)] or less.
The gas barrier film of the present invention is thus suitable for the transfer layer 30 having a low water vapor transmission rate, that is, having high gas barrier properties, while preventing cracking or the like of the inorganic layer 16 and maintaining high gas barrier properties. Can be transferred to

Moreover, in the gas barrier film of the present invention, the visible light transmittance of the transfer layer 30 provided with the gas barrier layer 18 and the release resin layer 20 from which the substrate 12 has been released is preferably 85% or more. The retardation value of the transfer layer 30 is preferably 30 nm or less.
By setting the visible light transmittance and retardation value of the transfer layer 30 in the above range, the gas barrier film of the present invention is transferred to seal a wavelength conversion film such as a quantum dot film or an optical member such as an organic EL element. In the case where the gas barrier property is imparted to the optical film such as a retardation film or the like, the sealing of the optical member or the gas barrier property can be imparted without affecting the optical performance of the transferred object. .

  Next, the material, the configuration, and the like of each component of the gas barrier film of the present invention will be described.

  As the substrate 12 in the gas barrier film 10, various known sheet-like materials used as substrates (supports) in various gas barrier films and various laminated gas barrier films can be used.

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

  In the present invention, necessary functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflective layer, a light shielding layer, a flattening layer, a buffer layer, a stress relaxation layer, and a release layer are provided on the surface of such a film. The substrate 12 may be formed with a layer (film) expressing

  Among them, the substrate 12 has a high elongation at break and can be made thinner because it is less likely to be broken during transport; it has a high melting point, is heat resistant, can easily peel at the interface with the release resin layer 20, and is inexpensive It is preferable that the release layer be 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 application of the gas barrier film 10, the forming material, and the like.
According to studies by 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 in the above range, the mechanical strength of the gas barrier film 10 can be sufficiently secured, and peeling can be easily performed at the time of transfer, etc., which is preferable.

  The organic layer 14 is a layer made of an organic compound, and basically, a monomer, an oligomer or the like to be the organic layer 14 is polymerized (crosslinked).

In the gas barrier film 10, the organic layer 14 functions as a base layer for appropriately forming the inorganic layer 16 that mainly exhibits gas barrier properties.
By having such an organic layer 14, the unevenness of the surface of the release resin layer 20 (or the lower inorganic layer 16), the foreign matter attached to the surface of the release resin layer 20, etc. are embedded, and the inorganic layer is formed. The 16 deposition surfaces can be made suitable for deposition of the inorganic layer 16. As a result, a region where the inorganic compound to be the inorganic layer 16 is not easily deposited, such as unevenness on the surface of the substrate 12 or unevenness due to the adhesion of foreign matter, is eliminated, and an appropriate inorganic layer 16 is formed over the entire surface of the substrate. Can be formed into a film, and the inorganic layer 16 having high gas barrier properties can be formed.

The glass transition temperature Tg of the organic layer 14 is preferably higher than the glass transition temperature Tg of the release resin layer 20, and is preferably 200 ° C. or more.
By setting it as the organic layer 14 which has high glass transition temperature Tg of 200 degreeC or more, it becomes possible to form the inorganic layer 16 into a film appropriately.
In addition, the organic layer 14 preferably has appropriate flexibility in order to prevent cracking and the like of the inorganic layer 16.
In the present invention, the glass transition temperature Tg may be measured in accordance with JIS K 7121.

In the gas barrier film 10, the forming material of 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, polyamide imide, polyether imide, cellulose acylate, polyurethane, poly Thermoplastic resins such as ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acrylic compound, etc., polysiloxane, and the like A film of an organosilicon compound is preferably exemplified. A plurality of these may be used in combination.

Among them, the organic layer 14 composed of a radical curable compound and / or a polymer of a cationic curable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.
Among them, acrylic resins and methacrylic resins mainly composed of acrylate and / or methacrylate monomers and oligomer polymers are preferable as the organic layer 14 in view of low refractive index, high transparency and excellent optical properties. Is exemplified.
Among them, bifunctional or more, particularly trifunctional or more, such as dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA) and dipentaerythritol hexa (meth) acrylate (DPHA). The acrylic resin and methacrylic resin which have polymers, such as a monomer and an oligomer of an acrylate and / or a methacrylate of these, as a main component are illustrated suitably. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.

Here, it is preferable that the forming material of the organic layer 14 be 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 respect to the peeling resin layer 20 can be easily adjusted by the irradiation amount of the ultraviolet ray or the electron beam, and the strong peeling force Can be realized. Therefore, it can be set as the structure which peels in the interface of the peeling resin layer 20 and the board | substrate 12. FIG.

The material for forming the organic layer 14 is a resin material containing 5% or more and less than 50% of monofunctional or more acrylates having an adamantane skeleton, or 5% or less and 50% or less of bifunctional or more acrylates having a fluorene skeleton. It is preferable that it is a resin material containing.
By using a resin material containing a monofunctional or more functional acrylate having an adamantane skeleton or a bifunctional or more functional acrylate having a fluorene skeleton as a forming material of the organic layer 14, curing shrinkage is maintained while maintaining a high glass transition temperature Tg The shrinkage rate at the time can be reduced, and the inorganic layer 16 formed on the organic layer 14 can be prevented from being broken.

  Such formation of the organic layer 14 may be formed (film formation) by a known method of forming a layer made of an organic compound in accordance with the organic layer 14 to be formed. A coating method is illustrated as an example.

That is, a coating composition containing an organic solvent, an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.) to be the organic layer 14, a crosslinking agent, etc. is prepared, and this coating composition is coated on the release resin layer 20. The coating film can be formed, and the coating film can be dried and cured to form the organic layer 14.
The organic layer 14 can be thinly formed by a coating method.

  In addition, as mentioned above, when it has several organic layer 14, the thickness of each organic layer 14 may be the same, or may mutually differ. Moreover, the forming 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 properties are mainly exhibited by the inorganic layer 16.

The forming material of the inorganic layer 16 is not limited, and various layers made of inorganic compounds exhibiting gas barrier properties can be used.
Specifically, metal oxides such as aluminum oxide, magnesium oxide, tantalum oxide, zirconium oxide, titanium oxide, indium tin oxide (ITO); metal nitrides such as aluminum nitride; metal carbides such as aluminum carbide; silicon oxide, Silicon oxides such as silicon oxynitride, silicon oxycarbide, silicon oxynitride carbide; silicon nitrides such as silicon nitride and silicon carbonitride; silicon carbides such as silicon carbide; hydrides of these; mixtures of two or more of these; Films made of inorganic compounds such as these hydrogen-containing substances are preferably exemplified. Also, mixtures of two or more of these are available.
In particular, metal oxides and nitrides, specifically silicon nitride, silicon oxide, silicon oxynitride, aluminum oxide, and a mixture of two or more of them can exhibit high transparency and can exhibit excellent gas barrier properties. In terms of point, it is suitably used. Among them, silicon nitride, silicon oxide, and a mixture thereof are preferably used because they have high gas barrier properties, high transparency, and high flexibility.

  Such formation of the inorganic layer 16 can be performed by CCP-CVD (capacitively coupled plasma chemical vapor deposition), ICP-CVD (inductively coupled plasma chemical vapor deposition) depending on the material of the inorganic layer 16 and the like. It may be carried out by a known vapor deposition method such as sputtering, vacuum evaporation and the like.

The thickness of the inorganic layer 16 may be determined as appropriate according to the material to be formed, by which the desired gas barrier properties can be exhibited. According to studies by the present 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.
By setting the thickness of the inorganic layer 16 to 10 nm or more, the inorganic layer 16 that stably exhibits sufficient gas barrier performance can be formed. In addition, the inorganic layer 16 is generally brittle, and if it is too thick, there is a possibility that cracking, cracks, peeling, etc. may occur. However, when the thickness of the inorganic layer 16 is 200 nm or less, cracking may occur. It can prevent.

  In addition, as mentioned above, when it has several inorganic layer 16, the thickness of each inorganic layer 16 may be same or different. Moreover, the forming material of each inorganic layer 16 may be the same or different.

In the gas barrier film 10, a release resin layer 20 is provided between the substrate 12 and the organic layer 14.
As described above, the peeling resin layer 20 is a resin layer in close contact with the organic layer 14 and capable of peeling from the substrate 12 at the interface with the substrate 12, and shears on the inorganic layer 16 when peeling the substrate 12. It is a layer that also functions as a stress relaxation layer that suppresses the application of force. In addition, after peeling of the substrate 12, the peeling resin layer 20 also functions as a support.

Here, it is preferable that the peeling resin layer 20 be low in water content and high in heat resistance.
As described above, the inorganic layer 16 exhibiting high gas barrier properties needs to be formed by vacuum film formation such as plasma CVD. If the release resin layer 20 has high water content, the degree of vacuum can not be increased because moisture is released even if evacuation is performed, and there is a possibility that the inorganic layer 16 can not be formed. In addition, even when the inorganic layer 16 is formed, when the release resin layer 20 expands and contracts due to absorption and release of moisture, the inorganic layer 16 may be broken, and high gas barrier properties may not be obtained. Therefore, it is preferable that the peeling resin layer 20 has low water absorption. Moreover, in order to form the inorganic layer 16 by plasma CVD etc., it is preferable that heat resistance is high.

  From the viewpoints of adhesion with the substrate 12 and the organic layer 14, water resistance, heat resistance, etc., as a material for forming the peeling resin layer 20, glass transition temperatures Tg of cycloolefin copolymer (COC), cycloolefin polymer (COP), etc. Is preferably a cyclic olefin resin of 100 ° C. or higher.

  Further, as described above, the organic layer 14 is formed on the release resin layer 20 by application. Therefore, from the viewpoint of the coating properties of the coating composition to be the organic layer 14, the solvent resistance, and the optical properties such as retardation, it is preferable to use cycloolefin copolymer (COC) as the material for forming the peeling resin layer 20. preferable.

Such a release resin layer 20 can be formed by the same coating method as the organic layer 14.
The release resin layer 20 can be formed thin by the application method.

The thickness of the release resin layer 20 may be appropriately set in accordance with the forming material of the release resin layer 20, the organic layer 14, the inorganic layer 16, and the substrate 12. According to the study of the present inventors, the thickness of the peeling resin layer 20 is preferably 0.1 to 25 μm, more preferably 0.5 to 15 μm, and particularly preferably 1 to 10 μm. preferable.
By setting the thickness of the peeling resin layer 20 to 0.1 μm or more, the 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, and 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 being broken.
Further, by setting the thickness of the peeling resin layer 20 to 25 μm or less, the occurrence of problems such as cracking of the peeling resin layer 20 and curling of the gas barrier film 10 due to the peeling resin layer 20 being too thick is suitably performed. The gas barrier film 10 can be easily rolled up.

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

Here, the thickness of the release resin layer 20 is preferably thicker than the thickness of the organic layer 14.
As described above, the organic layer 14 to be the base layer of the inorganic layer 16 needs to have higher heat resistance. Therefore, as a material for forming the organic layer 14, it is necessary to use a material having a higher glass transition temperature Tg. Here, in general, a material having a high glass transition temperature Tg is hard and difficult to stretch, so the thickness of the hard organic layer 14 is reduced and the thickness of the soft release resin layer 20 is increased, so that the release resin is The layer 20 can be properly functioned as a stress relaxation layer, and cracking of the inorganic layer 16 at the time of peeling the substrate 12 can be prevented to obtain high gas barrier properties.

Further, the peeling force between the peeling resin layer 20 and the substrate 12 and the organic layer 14 is not limited as long as the peeling force with the organic layer 14 is higher than the peeling force with the substrate 12.
Moreover, as for the peeling force of the peeling resin layer 20 and the board | substrate 12, 0.04 N / 25 mm-1 N / 25 mm are preferable.
By setting the peeling force between the peeling resin layer 20 and the substrate 12 in the above-mentioned range, it is possible to suppress the peeling force from being too weak and peeling during conveyance or the like, and the peeling force is too strong. It is possible to suppress disadvantages such as damage to the inorganic layer 16 at the time of peeling and deformation of the gas barrier film 10.
The peel strength (adhesion) may be measured in accordance with the 180 ° peel test method of JIS Z 0237.

  The organic protective layer 24 is a layer formed of an organic compound, is formed on the gas barrier layer 18 (inorganic layer 16), and protects the gas barrier layer 18.

  There is no limitation in particular in the formation material of the organic protective layer 24, Various known organic compounds similar to the organic layer 14 can be used.

Here, the organic protective layer 24 may be an adhesive layer having adhesiveness.
When the organic protective layer 24 has adhesiveness, when the transfer layer 30 is transferred to a transfer-receiving material, transfer can be easily performed without applying an adhesive or the like.
There is no limitation on the forming material of the organic protective layer 24 as the adhesive layer, and various known adhesive materials can be used.
It is preferable to use an acrylic pressure-sensitive adhesive as the pressure-sensitive adhesive material from the viewpoint of optical properties, particularly retardation and haze.
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 in accordance with the forming material of the organic protective layer 24 and the inorganic layer 16. According to the study of the present 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. preferable.
By setting the thickness of the organic protective layer 24 to 0.1 μm or more, the inorganic layer 16 can be properly protected. Moreover, the workability at the time of sticking the gas barrier film 10 to a to-be-transcribed body can be improved by the thickness of the organic protective layer 24 being 50 micrometers or less.

As the protective film 26, various known sheet-like materials used as known protective films can be used.
The film (resin film) which consists of various resin materials illustrated by the above-mentioned board | substrate 12 as an example is illustrated suitably.

Here, the material of the protective film 26 preferably has a Young's modulus of 6 GPa or less. The protective film 26 is stuck on the inorganic layer 16 which is the uppermost layer of the gas barrier layer 18 of the gas barrier film 10, and is separated from the inorganic layer 16 and used when the gas barrier film 10 is transferred. By setting the Young's modulus of the material forming the protective film 26 to 6 GPa or less, damage to the inorganic layer 16 when peeling off the protective film 26 can be more suitably prevented, and high gas barrier properties can be obtained.
In consideration of this point, LDPE, HDPE, PP, PET, PEN, PVC, PI and the like are suitably exemplified as a material for forming the protective film 26.

The thickness of the protective film 26 may be appropriately set according to the thickness required for the gas barrier film 10, the Young's modulus of the material of the protective film 26, and the like.
According to studies 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 suitably prevent damage to the inorganic layer 16 due to an impact or the like received from the outside during winding, etc., and to suppress wrinkles and deformation during transportation. Preferred.
By setting the thickness of the protective film 26 to 300 μm or less, it is preferable in that the gas barrier film 10 can be prevented from being unnecessarily thick.

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

Next, the transfer method of the gas barrier film of the present invention (also referred to as "the transfer method of the present invention") will be described.
The transfer method of the gas barrier film of the present invention adheres the surface opposite to the substrate of the gas barrier film to a substrate to be transferred, and peels the substrate to form a transfer layer comprising a gas barrier layer and a release resin layer. It is a transfer method of transferring to a transfer body.
Hereinafter, the transfer method of the present invention will be described with reference to FIGS. 4 (A) to 4 (C) and 5.

  4 (A) to 4 (C) use a gas barrier film 10b having an organic protective layer 24 as an adhesive layer as a gas barrier film as shown in FIG. An example of transfer to the retardation film 112 is shown.

First, as shown in FIGS. 4A and 4B, the surface of the gas barrier film 10b opposite to the substrate 12, that is, the organic protective layer 24 side is adhered to the retardation film 112 side. Match.
There is no limitation on the method of bonding, and various known methods for bonding film-like materials can be used. In addition, such bonding may be performed in sheet form, and bonding is performed by roll-to-roll (hereinafter also referred to as RtoR) using the long gas barrier film 10 and the retardation film 112. May be

In the illustrated example, although the gas barrier film has a pressure-sensitive adhesive layer, the present invention is not limited to this, and a pressure-sensitive adhesive is applied to a material to be transferred before bonding the gas barrier film. You may paste together.
In addition, in the case where the protective film 26 is provided on the organic protective layer 24 (or the inorganic layer 16), the protective film 26 may be peeled off and pasted to the substrate before being pasted to the substrate. .

Next, as shown in FIG. 4C, the substrate 12 is peeled off from the gas barrier film 10b attached to the retardation film 112.
There is no limitation on the peeling method of the substrate 12, and various known peeling methods of the film-like material can be used.
Also, such peeling of the substrate 12 may be performed in a sheet-like manner, or may be performed by RtoR.

In this manner, the transfer layer 30 of the gas barrier film 10b can be transferred to the retardation film 112, which is a transfer target, to obtain a retardation film 110 with a gas barrier layer as shown in FIG.
The transfer method of the gas barrier film of the present invention can prevent the inorganic layer from cracking at the time of peeling of the substrate 12, and therefore, the transfer layer 30 can be transferred to the transfer target while maintaining high gas barrier properties.
In addition, since the thickness of the transfer layer 30 can be made very thin, the influence on the optical characteristics such as transparency and retardation value can be reduced.

  In addition, in the present invention, there is no limitation in the transferred object which transfers a gas barrier film. It is suitably used for sealing of an optical member such as an organic EL element or a wavelength conversion material, which is required to have high gas barrier property, high transparency, low retardation, and excellent optical properties, and thus high gas barrier property is required. . Moreover, it is also possible to provide high gas barrier properties to various optical films and to utilize as an optical film and a gas barrier film.

Hereinafter, a member using the gas barrier film of the present invention will be described.
The retardation film with gas barrier layer 110 shown in FIG. 5 which is an example of the retardation film with gas barrier layer of the present invention using the gas barrier film of the present invention has an organic protective layer 24 and an inorganic layer on the retardation film 112. 16, a transfer layer 30 having an organic layer 14 and a release resin layer 20 is stacked.
Since the thickness of the transfer layer 30 of this retardation film 110 with a gas barrier layer is very thin, in addition to the optical characteristics of the retardation film itself, it is made a film having high gas barrier properties while suppressing the increase in thickness. be able to.

FIG. 6: is an example of the wavelength conversion film which transcribe | transferred the gas barrier film of this invention, and sealed the wavelength conversion layer.
The wavelength conversion film 100 shown in FIG. 6 includes a wavelength conversion layer 102, a gas barrier film 104 laminated on one side of the wavelength conversion layer 102, and a transfer layer 30 laminated on the other side of the wavelength conversion layer 102. Have.

The wavelength conversion layer 102 has a function of converting the wavelength of incident light and emitting it, and is, for example, a quantum dot layer formed by dispersing quantum dots in a binder such as a resin.
The type of quantum dot contained in the quantum dot layer is not particularly limited, and various known quantum dots may be appropriately selected according to the required wavelength conversion performance and the like.
Further, the type of binder contained in the quantum dot layer is not particularly limited, and various known binders may be appropriately selected according to the type of quantum dot, the 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 the gas barrier property required for sealing the wavelength conversion layer 102, and a known gas barrier film can be appropriately used. It is.

As shown in FIG. 6, the wavelength conversion film 100 is a transfer layer 30 in which one side of the wavelength conversion layer 102 is sealed with the conventional gas barrier film 104 and the other side is transferred from the gas barrier film 10 of the present invention. And sealed.
As described above, by sealing at least one surface of the wavelength conversion layer with the gas barrier film of the present invention, the thickness of the entire wavelength conversion film can be reduced.

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

  FIGS. 7A to 7C each show an example of the organic EL laminate in which the gas barrier film of the present invention is transferred to seal the organic EL element.

An organic EL laminate 120 a shown in FIG. 7A includes an element substrate 122, an organic EL element 124 formed on the element substrate 122, and a transfer layer 30 stacked on the organic EL element 124.
The element substrate 122 may be any element substrate used in various organic EL devices. Specifically, an element substrate made of glass, plastic, metal, ceramic or the like is exemplified. Further, in order to prevent the deterioration of the organic EL element 124 due to water or the like, it is preferable to be able to prevent the water or the like from passing through the element substrate 122 and reaching the organic EL element 124. Therefore, as the element substrate 122, it is preferable to use a substrate made of a material having low content of moisture and the like and low transmittance of moisture and the like, such as glass and metal.

  In addition, you may use the gas barrier film 10 (transfer layer 30) of this invention as an element substrate like the organic electroluminescent laminated body 120b shown to FIG. 7 (B). Or you may use what transferred the gas barrier film 10 of this invention to the resin base material as an element substrate.

The organic EL element 124 is, for example, a known organic EL element having an organic electroluminescent layer, and a transparent electrode and a reflective electrode which are an electrode pair for supporting the organic electroluminescent layer.
As shown in the figure, the organic EL element 124 is sealed by a 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 whole organic EL laminate can be reduced.

  The organic EL laminate may be a top emission type in which light is emitted from the transfer layer 30 side or a bottom emission type in which light is emitted from the element substrate 122 side.

Further, as in an organic EL laminate 120 c 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 the passivation film 126, and the transfer layer 30 may be transferred onto the passivation film 126.
The passivation film 126 is for preventing moisture, oxygen and the like from reaching the organic EL element 124 and deteriorating the organic EL element 124.
As such a passivation film 126, various films (layers) made of a material that exhibits gas barrier properties, which are used for known organic EL devices, can be used. Specifically, a film having the same gas barrier properties as the inorganic layer 16 and made of an inorganic compound such as silicon nitride and silicon oxide is exemplified.
The passivation film 126 may be formed by a known method according to the material for forming the film.

Hereinafter, with reference to FIG. 8 (A) and FIG. 8 (B), the manufacturing method of the gas barrier film of this invention is demonstrated.
In the following examples, as a preferred embodiment, the gas barrier film is produced by RtoR using a long substrate 12 and a protective film 26 or the like. As well known, with RtoR, an object to be treated is delivered from a roll formed by winding a long object to be treated, and processing such as film formation is carried out while being transported in the longitudinal direction, and the treated object is treated , It is a manufacturing method rolled in a roll again.

First, the peeling resin layer 20 is formed on the substrate 12 using a film forming apparatus conceptually shown in FIG.
Specifically, a coating composition containing an organic solvent, an organic compound to be the release resin layer 20, and the like is prepared.
On the other hand, a substrate roll Ra formed by winding a long substrate 12 in a roll shape is loaded at a predetermined position of the organic film forming apparatus shown in FIG. Next, the substrate 12 is fed from the substrate roll Ra and is passed through a predetermined path leading to the winding position. Furthermore, the coating composition that becomes the prepared release resin layer 20 is filled in a predetermined position of the coating unit 40. Note that reference numeral 48 in the drawing is a pair of transport rollers for transporting the substrate 12 along a predetermined path.
Then, the substrate 12 is fed from the substrate roll Ra and transported in the longitudinal direction, and the coating composition prepared in the coating unit 40 is coated on the substrate 12, and then the coating composition is dried in the drying unit 42. Furthermore, ultraviolet light irradiation, heating, etc. are performed in the hardening part 44 as needed, and the peeling resin layer 20 is formed. Furthermore, the long film in which the peeling resin layer 20 was formed on the board | substrate 12 is wound in roll shape, and it is set as the base material roll Rb.
In addition, although illustration is abbreviate | omitted, after forming the peeling resin layer 20 as a preferable aspect, a protective film is laminated | stacked and it winds up after that, and it is set as the base-material roll Rb.

Next, the organic layer 14 is formed on the release resin layer 20 of the film formation substrate Za using the substrate 12 on which the release resin layer 20 is formed as the film formation substrate Za. The formation of the organic layer 14 may be basically performed in the same manner as the formation of the peeling resin layer 20 using an organic film forming apparatus as shown in FIG. 8A.
That is, a coating composition containing an organic solvent, an organic compound to be the organic layer 14, a polymerization initiator and the like is prepared.
In addition, a base material roll Rb formed by winding a long film-forming base material Za in a roll shape is loaded at a predetermined position of the organic film forming apparatus shown in FIG. Next, the film-forming substrate Za is fed from the substrate roll Rb, and is passed through a predetermined path leading to the winding position. Furthermore, the coating composition to be the prepared organic layer 14 is filled in a predetermined position of the coating unit 40.
Then, the film-forming substrate Za is fed from the substrate roll Rb, and while being transported in the longitudinal direction, the coating composition prepared in the coating unit 40 is coated on the release resin layer 20 and then the drying unit 42 The coating composition is dried in the step (b), and the organic compound is polymerized (crosslinked) in the curing section 44 by irradiation with ultraviolet light or the like to form the organic layer 14. Furthermore, the long film-forming base material Za which formed the organic layer 14 is wound in roll shape, and it is set as the base material roll Rc.

A protective film may be attached to the organic layer 14 after the formation of the organic layer 14. Adhesion of the protective film is preferably performed before the organic layer 14 contacts another member such as a guide roller.
Thereby, damage to the organic layer 14 which is the base layer of the inorganic layer 16 can be prevented, and the inorganic layer 16 can be appropriately formed on the smooth organic layer 14, so that a gas barrier film expressing high gas barrier properties can be obtained. Can.
Moreover, although it was set as the structure which performs film-forming of the peeling resin layer 20, and film-forming of the organic layer 14 in the said example, it is not limited to this, It does not perform winding after film-forming of the peeling resin layer. Subsequently, the organic layer 14 may be formed. That is, in the transport path of the substrate 12, the coating unit 40 for forming the release resin layer 20, the drying unit 42 and the curing unit 44, and the coating unit 40 for forming the organic layer 14, the drying unit 42 and the curing The film formation of the peeling resin layer 20 and the film formation of the organic layer 14 may be continuously performed using a film formation apparatus in which the portion 44 is disposed.

Next, in the inorganic film forming apparatus as schematically shown in FIG. 8B, the inorganic layer 16 is formed on the substrate 12 (substrate for film formation Zb) on which the release resin layer 20 and the organic layer 14 are formed, The protective film 26 is attached to the inorganic layer 16 to produce the gas barrier film 10.
The inorganic film forming apparatus shown in FIG. 8 (B) forms the inorganic layer 16 by, for example, CCP-CVD (capacitively coupled plasma chemical vapor deposition), and includes a supply chamber 50 and a film forming chamber 52. And a winding room 54.
First, the base material roll Rc is loaded at a predetermined position of the supply chamber 50. Then, the film-forming substrate Zb is fed out from the substrate roll Rc, and passes through a predetermined path from the supply chamber 50 through the film forming chamber 52 to the winding chamber 54. The base material roll Rc is loaded such that the organic layer 14 is a film forming surface in the film forming chamber 52.
Further, the protective film roll 26R is loaded at a predetermined position of the film forming chamber 52. Then, the protective film 26 is fed out from the protective film roll 26R, and a predetermined path from the film forming chamber 52 to the winding chamber 54 is passed.

Next, the supply chamber 50 is evacuated by the vacuum evacuation unit 50a, the film forming chamber 52 by the vacuum evacuation unit 52a, and the winding chamber 54 by the vacuum evacuation unit 54a, and each chamber is depressurized to a predetermined pressure.
When the pressure in each chamber reaches a predetermined pressure, transport of the film-forming substrate Zb and the protective film 26 is started.

The film-forming substrate Zb is fed from the base material roll Rc, guided by the guide roller 58, and conveyed to the film forming chamber 52.
The film-forming substrate Zb conveyed to the film forming chamber 52 is guided by the guide roller 60 and wound around the circumferential surface of the cylindrical drum 62. The drum 62 also acts as an electrode in CCP-CVD. The drum 62 has a temperature control function as a preferred embodiment. The film-forming substrate Zb is transported on a predetermined path by the drum 62, and is formed by CCP-CVD by a film forming means having the electrode pair consisting of the drum 62 and the shower electrode 64, the raw material gas supply unit 68 Thus, the inorganic layer 16 is formed, and a combination film of the peeling resin layer 20, the organic layer 14, and the inorganic layer 16 is formed on the substrate 12.
The formation of the inorganic layer 16 by plasma CVD may be performed by a known method according to the forming material of the inorganic layer and the like. In addition to CCP-CVD, the inorganic layer 16 can be formed by various known vapor phase deposition methods such as ICP-CVD (inductively coupled plasma chemical vapor deposition), sputtering, vacuum deposition, etc. It is.

On the other hand, in synchronization with the transport of the film-forming substrate Zb, the protective film 26 is fed from the protective film roll 26R and transported in the longitudinal direction.
The film-forming substrate Zb on which the inorganic layer 16 is formed and the protective film 26 are laminated and pressure-bonded by the laminating roller pair 72, whereby the gas barrier film 10 is produced.
An adhesive layer may be formed on the surface of the protective film 26 facing the inorganic layer 16.

When producing the gas barrier film 10 by RtoR, it is preferable to apply the protective film 26 after forming the inorganic layer 16 and before the inorganic layer 16 contacts another member such as a guide roller.
Thereby, the damage of the inorganic layer 16 can be prevented and the gas barrier film 10 which expresses the target gas barrier property can be obtained.

  In the film forming chamber 52, the gas barrier film 10 produced by laminating and sticking the laminated film and the protective film 26 by the laminating roller pair 72 is conveyed from the film forming chamber 52 to the winding chamber 54 and is guided by the guide roller 76. It is guided to a predetermined path, wound up, and made into a barrier film roll Rd in which the long gas barrier film 10 is wound.

In addition, when the film-forming base material Zb has a protective film on the organic layer 14, if the protective film is peeled and the inorganic layer 16 is formed before the inorganic layer 16 is formed. Good.
The peeling of the protective film is preferably performed at a position where there is no member such as a guide roller in contact with the organic layer 14 in the path leading to the film forming means of the inorganic layer 16.

  In the case where the organic protective layer 24 is further formed on the inorganic layer 16, the substrate 12 on which the peeling resin layer 20, the organic layer 14 and the inorganic layer 16 are formed is shown in FIG. It may be formed in the same manner as the peeling resin layer 20 and the organic layer 14 using an organic film forming apparatus as shown in 2.).

  As mentioned above, although the gas barrier film of the present invention was explained in detail, the present invention is not limited to the above-mentioned embodiment, but various improvement and change may be made in the range which does not deviate from the gist of the present invention, Of course.

  Hereinafter, the present invention will be described in more detail by way of specific examples of the present invention.

Example 1
As Example 1, a gas barrier film 10a shown in FIG. 1 (A) was produced.

<Formation of Release Resin Layer 20>
As the substrate 12, a long PET film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) having a width of 1000 mm, a thickness of 50 μm, and a length of 100 m was used.
A release resin layer 20 was formed on the unprimed surface side of the substrate 12 according to the following procedure.

As coating liquid A1 used as the exfoliation resin layer 20, a coating liquid prepared by dissolving COC resin (APEL 6015T manufactured by Mitsui Chemicals, Inc.) with cyclohexane and adjusting the solid content concentration to 10% was used.
The coating solution A1 is filled in the coating unit 40 of the RtoR film forming apparatus as shown in FIG. 8A, and a substrate roll Ra formed by winding the substrate 12 in a roll is loaded at a predetermined position. Then, the substrate 12 was inserted into a predetermined transport path. The coating unit 40 used a die coater.
Then, while transporting the substrate 12 in the longitudinal direction, the coating unit A applies the coating solution A1 to the substrate 12 so that the dry film thickness becomes 2 μm, and the drying unit 42 in the drying unit 40 for 3 minutes at a drying temperature of 100 ° C. The release resin layer 20 was formed on the substrate 12 by drying. At this time, the cured portion 44 was not used.
That is, the formation material of the peeling resin layer 20 is a cycloolefin copolymer.

  It was 145 degreeC when it measured based on JISK7121 by glass transition temperature Tg of the peeling resin layer 20 formed with the high sensitivity type | mold differential scanning calorimeter (The Hitachi High-Tech Science company make, DSC7000X).

<Formation of Organic Layer 14>
Next, the organic layer 14 was formed on the release resin layer 20 formed in the following procedure.
A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a photopolymerization initiator (Irg 819 manufactured by BASF Japan) are prepared as a coating solution B1 to be the organic layer 14 and weighed to have a weight ratio of 97: 3, These were dissolved in methyl ethyl ketone to prepare a coating solution having a solid concentration of 15%.

The coating solution B1 is filled in the coating unit 40 of the RtoR film forming apparatus as shown in FIG. 8A, and the substrate 12 (substrate for film formation Za) having the peeling resin layer 20 is formed into a roll. The wound base roll Rb was loaded at a predetermined position, and the film-forming base Za was inserted into a predetermined transport path. The coating unit 40 used a die coater.
Then, while transporting the film-forming substrate Za in the longitudinal direction, the coating section B applies the coating solution B1 on the release resin layer 20 of the film-forming substrate Za to a dry film thickness of 1 μm. The drying unit 42 is dried at a drying temperature of 50 ° C. for 3 minutes, and the curing unit 44 is irradiated with ultraviolet rays (total irradiation amount of about 700 mJ / cm ² ) and cured to form the organic layer 14 on the release resin layer 20. Formed.
In addition, before contacting the roll which contacts the surface by the side of the organic layer 14 first after hardening the organic layer 14, it wound up after sticking the protective film of polyethylene on the organic layer 14.

  When the glass transition temperature Tg of the formed organic layer 14 was measured by a high sensitivity type differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Co., Ltd.) according to JIS K 7121, it was a measurement limit of 250 ° C. or more.

<Formation of Inorganic Layer 16>
Next, the inorganic layer 16 was formed on the formed organic layer 14 in the following procedure.
The substrate 12 (substrate for film formation Zb) on which the peeling resin layer 20 and the organic layer 14 are formed is wound in a roll shape at a predetermined position of the supply chamber 50 of the film forming apparatus as shown in FIG. The base roll Rc was loaded, and the protective film roll 26R was loaded at a predetermined position of the film forming chamber 52. Further, the film-forming substrate Zb was fed from the substrate roll Rc, and was passed through a predetermined conveyance path from the supply chamber 50 through the film forming chamber 52 to the winding chamber 54. Further, the protective film 26 was fed from the protective film roll 26R, and was passed through a predetermined conveyance path from the film forming chamber 52 to the winding chamber 54.
In this state, the film-forming substrate Zb and the protective film 26 are conveyed synchronously, and after passing through the film surface touch roll just before film formation, the protective film is peeled off from the film-forming substrate Zb A silicon nitride film was formed as the inorganic layer 16 on the surface of the organic layer 14 of the film-forming substrate Zb supported / guided by the drum 62 in 52 by CCP-CVD. Next, the protective film 26 was laminated and attached onto the inorganic layer 16 by the laminating roller pair 72, and a gas barrier film 10a as shown in FIG. 1 was produced and wound up.

For forming the inorganic layer 16, silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm) and hydrogen gas (flow rate 2000 sccm) were used as source gases. The power supply was a high frequency power supply with a frequency of 13.56 MHz, and the plasma excitation power was 8 kW. The deposition pressure was 40 Pa. The film thickness of the inorganic layer 16 was 30 nm.
The adhesion of the protective film 26 was performed after the inorganic layer 16 was formed and before the inorganic layer 16 contacted other members. In addition, a polyethylene film was used as the protective film 26.

Example 2
Furthermore, a gas barrier film 10 b as shown in FIG. 2A 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.

Urethane skeleton acrylic polymer (Akrit 8BR930 manufactured by Taisei Fine Chemical Co., Ltd.), photopolymerization initiator (Irg 184 manufactured by BASF Japan), silane coupling agent (Shin-Etsu Silicone Co., Ltd. KBM5103), and softening as a coating liquid C1 to be the organic protective layer 24 Byron U1400 (manufactured by Toyobo Co., Ltd.) was weighed to have a weight ratio of 78: 10: 10: 2, and dissolved in methyl ethyl ketone to prepare a coating solution having a solid content concentration of 15%.
The coating liquid C1 is filled in the coating portion 40 of the RtoR film forming apparatus as shown in FIG. 8A, and the substrate 12 on which the peeling resin layer 20, the organic layer 14 and the inorganic layer 16 are formed A substrate roll formed by winding the film base Zc) in a roll was loaded at a predetermined position, and the film-forming base Zd was inserted into a predetermined transport path. The coating unit 40 used a die coater.
Then, while transporting the film-forming substrate Zc in the longitudinal direction, the coating section C applies the coating solution C1 on the inorganic layer 16 of the film-forming substrate Zc to a dry film thickness of 1 μm. The drying unit 42 is dried at a drying temperature of 100 ° C. for 3 minutes, and the curing unit 44 is irradiated with ultraviolet rays (total irradiation amount of about 600 mJ / cm ² ) and cured to form the organic protective layer 24 on the inorganic layer 16. It formed.

[Example 3]
As a coating solution for forming the organic protective layer 24, the following coating solution C2 is used, the thickness of the organic protective layer 24 is 3 μm, and after forming the organic protective layer 24, similarly to the above, the first film surface touch roll is used. A gas barrier film 10c as shown in FIG. 2 (B) was produced in the same manner as in Example 2 except that a separator film (a film binder BD manufactured by Fujimori Kogyo Co., Ltd.) was attached as the protective film 26.
Coating solution C2 was prepared by adding 100 parts of 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 diluting with butyl acetate. Prepared.
The 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 for forming the organic protective layer 24.

[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 peeling resin layer 20.
The coating liquid A2 was prepared by dissolving a COC resin (APEL 6509T manufactured by Mitsui Chemicals, Inc.) in cyclohexane so as to have a solid content concentration of 10%.
It was 70 degreeC, when the glass transition temperature Tg of the formed peeling resin layer 20 was measured similarly to the above.

[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 peeling resin layer 20.
The coating liquid A3 was prepared by dissolving COC resin (APEL 6011T, manufactured by Mitsui Chemicals, Inc.) with cyclohexane so that the solid content concentration was 10%.
The glass transition temperature Tg of the release resin layer 20 thus formed was measured in the same manner as above, and it was 105.degree.

[Example 7]
A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution A4 was used as the coating solution to be the release resin layer 20.
The coating solution A4 was prepared by dissolving COP resin (Atodon D4540 manufactured by JSR Corporation) with cyclohexane so that the solid concentration would be 10%.
The glass transition temperature Tg of the release resin layer 20 formed was measured in the same manner as above, and it was 128.degree.

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

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

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

[Example 11]
A gas barrier film 10a was produced in the same manner as in Example 1 except that the solid concentration and coating amount of the coating liquid A1 to be the peeling resin layer 20 were changed, and the dry film thickness was 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 prepared by blending A-DPH (Tin 250C or higher, manufactured by Shin-Nakamura Chemical Co., Ltd.) and A-600 (Tg-22C, manufactured by Shin-Nakamura Chemical Co., Ltd.) to 4: 1. A photopolymerization initiator (Irg 819, manufactured by BASF Japan) was weighed so as to be 97: 3 in weight ratio, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%.
It was 180 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured similarly to the above.

[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 solution B3 is prepared by blending A-DPH (Tin 250C or higher, manufactured by Shin-Nakamura Chemical Co., Ltd.) and A-600 (Tg-22C, manufactured by Shin-Nakamura Chemical Co., Ltd.) in a ratio of 1: 1. A photopolymerization initiator (Irg 819, manufactured by BASF Japan) was weighed so as to be 97: 3 in weight ratio, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%.
It was 114 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured similarly to the above.

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 prepared by weighing EB 3702 (Tg 53 ° C.) manufactured by Daicel Ornex Co., Ltd. and a photopolymerization initiator (Irg 819 manufactured by BASF Japan) to a weight ratio of 97: 3, dissolving these in methyl ethyl ketone The concentration was adjusted to 15%.
It was 53 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured similarly to the above.

[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 blended so that A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd. Tg 250 ° C. or higher) and 1-ADMA (1-adamantyl methacrylate Osaka Organic Chemical Industry Co., Ltd. Tg 250 ° C.) become 1: 1. This and a photopolymerization initiator (Irg 819, manufactured by BASF Japan) were weighed so as to be 97: 3 in weight ratio, dissolved in methyl ethyl ketone, and adjusted to a solid content concentration of 15%.
That is, the forming material of the organic layer contains a monofunctional or more functional acrylate having an adamantane skeleton.
It was 250 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured similarly to the above.

[Example 16]
A gas barrier film 10a was produced in the same manner as in Example 1 except that the following coating solution B6 was used as the coating solution to be the organic layer 14.
The coating solution B6 was prepared by blending A-DPH (a Tg of 250 ° C. or more manufactured by Shin-Nakamura Chemical Co., Ltd.) and EA-200 (an acrylate monomer: Tg 211 ° C. manufactured by Osaka Gas Chemical Co., Ltd.) The polymerization initiator (Irg 819, manufactured by BASF Japan) was weighed so as to be 97: 3 and dissolved in methyl ethyl ketone to prepare a solid content concentration of 15%.
That is, the material for forming the organic layer contains a bifunctional or higher functional acrylate having a fluorene skeleton.
It was 230 degreeC when the glass transition temperature Tg of the formed organic layer 14 was measured similarly to the above.

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

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

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

[Example 20]
A gas barrier film 10a was produced in the same manner as in Example 1 except that a silicone release film (film bina BD manufactured by Fujimori Kogyo Co., Ltd.) was used as the substrate 12.

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

Example 22
A gas barrier film 10c was produced in the same manner as in Example 3 except that the solid concentration and application amount of the coating liquid C2 to be the organic protective layer 24 were changed to make the film thickness 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 was not formed.

Comparative Example 2
When forming the release resin layer, after drying, ultraviolet rays were irradiated at an accumulated irradiation amount of about 3000 mJ / cm ² , cured and wound up. Next, a gas barrier film was produced in the same manner as in Example 1 except that the integrated irradiation amount of ultraviolet light when forming the organic layer was changed to about 50 mJ / cm ² .
Thereby, the peeling force between the peeling resin layer and the substrate is strengthened, and the peeling force between the organic layer and the peeling resin layer is weakened, so that the peeling force between the organic layer and the peeling resin layer is It was weaker than the peeling force with the substrate. That is, peeling was performed between the peeling resin layer and the organic layer.

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

<Gas barrier properties>
(Transfer process)
As a material to be transferred, a TAC film with a pressure-sensitive adhesive layer of 200 mm square was prepared by bonding an optical adhesive film (manufactured by PDS1 Panac Corporation) to Fujitac (TD80 manufactured by Fuji Film Co., Ltd.).
After peeling off the protective film 26 of the produced gas barrier film 10, it was bonded by a laminator (Proteus manufactured by Faroe's) so that the adhesive layer of the transferred body and the inorganic layer 16 of the gas barrier film 10 were in contact. The lamination pressure was 0.5 MPa and the transfer speed was 5 m / min.
After bonding, the substrate 12 of the gas barrier film 10 was peeled off.
To peel off the substrate 12, first, a 200 mm square bonding film is punched into 100 mm square using a Thomson blade to ensure that the end face is peeled off, and the TAC film side is down, and the TAC film surface is high Then, apply an adhesive tape (Nitto cello tape (registered trademark)) for grasping the substrate 12 by 2 cm to the end, and make the tape parallel to the sample so that the substrate 12 draws a circular arc in the same way as the 180 degree peel test. It was peeled off by pulling it. The peeling was performed under the environment of temperature 25 ° C. and humidity 50% RH.
In Examples 3, 4, 21 and 22 having the organic protective layer 24 to be the adhesive layer on the inorganic layer 16, Fujitac (TD80 made by Fuji Film Co., Ltd.) to which the adhesive film is not bonded is transferred The transcription was performed in the same manner except for the body.

(Water vapor permeability measurement)
The water vapor transmission rate of the gas barrier film transferred to the transfer target and the substrate 12 was peeled was measured by the calcium corrosion method (the method described in JP-A-2005-283561). The conditions of constant temperature and humidity processing were a temperature of 40 ° C. and a relative humidity of 90% RH.
In addition, the water vapor transmission rate of Fujitac alone was 400 [g / (m ² · day)].
Based on the measured water vapor transmission rate, evaluation was made according to the following criteria.
A: Water vapor transmission rate is less than 5 × 10 ⁻⁵ [g / (m ² · day)] B: Water vapor transmission rate is 5 × 10 ⁻⁵ or more and 1 × 10 ⁻⁴ [g / (m ² · day)] less than C: Water vapor transmission rate is 1 × 10 ^{-4 to} 5 × 10 ^-4 [g / (m ² · day)] D: Water vapor transmission rate is 5 × 10 ^{-4 to} 1 × 10 ^-3 [g / (m) ² · day)] less than E: water vapor transmission rate 1 × 10 ^-3 [g / (m ² · day)] or more

<Optical characteristics>
After peeling off the protective film 26 of the produced gas barrier film, the substrate 12 is peeled off, and the transfer layer 30 including the release resin layer 20 and the gas barrier layer 18 (organic layer 14 and inorganic layer 16) is taken out. The total light transmittance and retardation value were measured.
(Total light transmittance)
The total light transmittance of the removed transfer layer 30 was measured using a spectrophotometer.
The following criteria evaluated based on the measured total light transmittance.
A: total light transmittance 90% or more B: total light transmittance 88% to less than 90% C: total light transmittance 86% to less than 88% D: total light transmittance 84% to 86 %Less than

(Retardation value)
The retardation value of the transfer layer 30 taken out was measured by KOBRA-WR (manufactured by Oji Scientific Instruments).
The following criteria evaluated based on the measured retardation value.
A: Retardation value of 5 nm or less B: Retardation value of more than 5 nm and 10 nm or less C: Retardation value of more than 10 nm and 20 nm or less D: Retardation value of more than 20 nm The results are shown in the following table.

As shown in Table 1 above, the embodiment of the present invention having a peeling resin layer between the substrate and the gas barrier layer and peeling at the interface between the peeling resin layer and the substrate is a gas barrier as compared to the comparative example. It is understood that the properties and the optical properties are excellent.
Further, it is understood from the comparison of Examples 1, 5 and 6 that the release resin layer is preferably a cyclic olefin resin having a glass transition temperature Tg of 100 ° C. or higher.
Further, from the comparison between Example 1 and Example 7, it is understood that the release resin layer is preferably a cycloolefin copolymer.
Moreover, it turns out that 0.1-25 micrometers is preferable and 0.5-15 micrometers is more preferable from contrast of Example 1 and 8-11.

Moreover, it turns out that 200 degreeC or more is preferable for the glass transition temperature Tg of an organic layer from contrast of Example 1, 12-14.
Further, from the comparison of Examples 1, 15 and 16, the organic layer preferably contains 5% or more and less than 50% of one or more functional acrylates having an adamantane skeleton, or a bifunctional or more acrylate having a fluorene skeleton. It is understood that it is preferable to contain 5% or more and less than 50%.
Further, from the comparison of Examples 1, 18 and 19, it is understood that the thickness of the organic layer is preferably 0.1 to 50 μm, and more preferably 0.2 to 3 μm.
Further, from the comparison between Example 1 and Example 17, it is understood that the inorganic layer is preferably silicon nitride.

Further, it is understood from Examples 2 to 4, 21 and 22 that it is preferable to have the organic protective layer 24 on the inorganic layer 16.
Further, from the comparison between Example 3 and Example 4, it is understood that it is preferable to use an acrylic pressure-sensitive adhesive as the organic protective layer 24.
Further, it is understood from the comparison 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 as shown in FIG. 6 was produced using the produced gas barrier film. 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 polypropylene filter having a pore size of 0.2 μm, and then 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.
(Quantum dot-containing polymerizable composition A)
-Toluene dispersion of quantum dot 1 (emission maximum: 520 nm) 10.0 parts by mass-Toluene dispersion of quantum dot 2 (emission maximum: 630 nm) 1.0 parts by mass-lauryl methacrylate 80.8 parts by mass-trimethylolpropane 18.2 parts by mass of triacrylate, 1.0 part by mass of a photopolymerization initiator (IRGACURE 819 (manufactured by BASF))

<Production of quantum dot film>
Using the gas barrier film of Example 1 as the first film, the protective film 26 on the inorganic layer 16 is peeled off while continuously conveying at a tension of 1 m / min and 60 N / m, and the above is prepared on the inorganic layer 16 The applied composition was applied by a die coater to form a coating of 50 μm in thickness.
Then, the film on which the coating film is formed is wound on a backup roller, and the second film (having the same configuration as the first film) is peeled off the protective film on the coating film, and the inorganic layer 16 is coated It laminated in the direction which touches, and the coating film was pinched with the 1st film and the 2nd film.
After passing continuously through a heating zone at 60 ° C. for 3 minutes in this state, ultraviolet rays are irradiated and cured using a 160 W / cm air-cooled metal halide lamp (manufactured by I-Graphics Co., Ltd.). Were formed (wavelength conversion layer 102). In addition, the irradiation amount of an ultraviolet-ray was 2000 mJ / cm < ² >.
The substrate 12 of the first film and the second film was peeled off to produce a quantum dot film (wavelength conversion film 100).

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

Specifically, the brightness of the wavelength conversion film immediately after preparation and the brightness after being left for 1000 hours in an environment of temperature 60 ° C. and humidity 90% RH were measured, and the durability was evaluated from the amount of change.
The measurement of the brightness was performed as follows.
First, a commercially available liquid crystal display device (Amazon's Kindle Fire HDX 7 ") was disassembled, and a backlight unit provided with a blue light source was taken out. Next, a wavelength conversion film cut out in a rectangular shape on the light guide plate of the backlight unit The two prism sheets taken out from the liquid crystal display were placed on top of each other so that the directions of the concavo-convex patterns on the surface were orthogonal to each other.
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 of the backlight unit.

  As a result of 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 produced gas barrier film was used to produce a retardation film 110 with a gas barrier layer as shown in FIG.
As the retardation film 112, special polycarbonate W138 (manufactured by Teijin Limited) was used.
First, an optical adhesive film (manufactured by PDS1 PANAC CO., LTD.) Was bonded to the retardation film 112.
Next, the protective film 26 of the gas barrier film 10 of Example 1 is peeled off, and then the adhesive layer side of the retardation film 112 is in contact with the inorganic layer 16 of the gas barrier film 10 using a laminator (Proteus manufactured by Ferroes) I put it together. After bonding, the substrate 12 of the gas barrier film 10 was peeled off to prepare a retardation film 110 with a gas barrier layer.

[Evaluation]
The optical properties of the produced gas barrier layer-equipped retardation film 110 of Example 24 were evaluated.

  Specifically, when the retardation values of the retardation film 112 alone and the retardation film 110 with a gas barrier layer were measured, the difference was 2% or less. Therefore, it is understood that the retardation film with a gas barrier layer to which the gas barrier film of the present invention has been transferred maintains high optical properties and has high gas barrier properties.

[Example 25]
Using the produced gas barrier film, an organic EL laminate 120a as shown in FIG. 7 (A) was produced.

<Fabrication of organic EL element>
A glass plate having a thickness of 500 μm and a size of 20 × 20 mm was prepared as an element substrate 122.
The peripheral 2 mm of this element substrate was masked by ceramic. Furthermore, the element substrate subjected to masking was loaded into a general vacuum deposition apparatus, and an electrode made of metallic aluminum having a thickness of 100 nm was formed by vacuum deposition, and a lithium fluoride layer having a thickness of 1 nm was further formed. . Subsequently, the following organic compound layers were sequentially formed by vacuum evaporation on the element substrate on which the electrode and the lithium fluoride layer were formed.
· (Emitting layer and electron transporting layer) tris (8-hydroxyquinolinato) aluminum: film thickness 60 nm
-(Second hole transport layer) N, N'-diphenyl-N, N'-dinaphthylbenzidine: film thickness 40 nm
-(First hole transport layer) Copper phthalocyanine: 10 nm film thickness
Further, the element substrate on which these layers are formed is loaded into a general sputtering apparatus, and 0.2 μm thick ITO thin film is formed by DC magnetron sputtering using ITO (Indium Tin Oxide indium tin oxide) as a target. The transparent electrode which consists of these was formed, and the organic EL element 124 which is a light emitting element using organic EL material was formed.

<Transfer of gas barrier film>
Next, the 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 from which the masking was 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 side facing the adhesive surface, and then the substrate of the gas barrier film 10a is peeled off. A laminate 120a was produced.

[Example 26]
After removing the masking, the element substrate 122 on which the organic EL element 124 is formed is loaded into a general plasma CVD apparatus, and a 1500 nm-thick passivation film 126 made of silicon nitride is formed by plasma CVD (CCP-CVD). An organic EL laminate 120c as shown in FIG. 7C was produced in the same manner as in Example 25 except for forming an organic EL laminate.

[Example 27]
An organic EL laminate was produced in the same manner as in Example 25 except that the gas barrier film 10 of Example 1 was used as an element substrate.
Specifically, the gas barrier film of Example 1 is transferred to a TAC film with an adhesive layer in which an optical adhesive film (PDS1 PANAC Corporation) is bonded to Fujitac (TD80 manufactured by Fuji Film Co., Ltd.), and the substrate 12 is The peeled laminate was used as an element substrate, and the organic EL element 124 was formed on the peeling resin layer 20.
Thereafter, in the same manner as described above, the organic EL element 124 was sealed with another gas barrier film 10 to produce an organic EL laminate.

[Evaluation]
Durability was evaluated about the manufactured organic electroluminescent laminated body of Examples 25-27.

Specifically, the manufactured organic EL laminate was left for 200 hours in an environment of a temperature of 60 ° C. and a humidity of 90% RH. After standing, each organic EL laminate was caused to emit light by applying a voltage of 7 V using a SMU2400 source-measure unit manufactured by Keithlel. It observed from the gas barrier film side with the microscope, confirmed the presence or absence of generation | occurrence | production of a dark spot, and evaluated it by the following references | standards.
A: Occurrence of dark spots was not observed at all B: Occurrence of dark spots was slightly observed C: Occurrence of dark spots was clearly recognized D: Area ratio of dark spots was larger Evaluation As a result, the organic EL laminates of Examples 25 to 27 were all A.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10 gas-barrier film 12 board | substrate 14 organic layer 16 inorganic layer 18 gas-barrier layer 20 peeling resin layer 24 organic protective layer 26 protective film 30 transfer layer 40 application part 42 drying part 44 hardening part 48 conveyance roller pair 50 supply chamber 50a, 52a, 54a vacuum Evacuating means 52 film forming chamber 54 winding chamber 58, 60, 76 guide roller 62 drum 64 shower electrode 68 raw material gas supply unit 70 high frequency power source 72 laminated roller pair 100 wavelength conversion film 102 wavelength conversion layer 104 gas barrier film 110 gas barrier layer attached Retardation film 112 Retardation film 120 Organic EL laminate 122 Element substrate 124 Organic EL element 126 Passivation film

Claims (19)

A substrate,
A gas barrier layer having at least one combination of an inorganic layer and an organic layer to be a surface on which the inorganic layer is provided, provided on one surface of the substrate;
And a release resin layer provided between the substrate and the gas barrier layer, in close contact with the organic layer, and for peeling the substrate from the substrate.
The organic layer is thinner than the peeling resin layer, a glass transition temperature of the organic layer is rather higher than the glass transition temperature of the release resin layer,
The material for forming the release resin layer is a cycloolefin copolymer,
The forming material of 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,
It is characterized in that the forming material of the organic layer contains 5% or more and less than 50% of monofunctional or more acrylates having an adamantane skeleton or 5% or more and less than 50% of bifunctional or more acrylates having a fluorene skeleton. Gas barrier film.   The gas barrier film according to claim 1, 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. The gas barrier film according to claim 1 or 2 thickness of the peeling resin layer is 0.1～25Myuemu. The gas barrier film according to any one of claims 1 to 3 , wherein a forming material of the inorganic layer is silicon nitride, silicon oxide, or a mixture thereof. The thickness of the organic layer, the gas barrier film according to any one of claims 1 to 4, which is 0.1 to 5 [mu] m. The gas barrier film according to any one of claims 1 to 5 , wherein a protective film or an organic protective layer is provided on the gas barrier layer. The gas barrier film according to claim 6 , wherein the organic protective layer is an acrylic adhesive. The gas barrier film according to claim 6 or 7 having a protective film on the organic protective layer. The thickness of the said organic protective layer is 0.1-50 micrometers, The gas barrier film as described in any one of Claims 6-8 . The gas barrier film according to any one of claims 1 to 9 , wherein the substrate is a polyethylene terephthalate film provided with a release layer. 11. The gas barrier according to any one of claims 1 to 10 , wherein the water vapor transmission rate of the transfer layer comprising the gas barrier layer and the release resin layer from which the substrate has been peeled is less than 0.01 g / (m ² · day). the film. The gas barrier film according to any one of claims 1 to 11 , wherein the visible light transmittance of the transfer layer comprising the gas barrier layer and the release resin layer from which the substrate has been peeled is 85% or more and the retardation value is 30 nm or less. . From said substrate of the gas barrier film according to any one of claims 1 to 12 adhered to the surface opposite to the transfer member, by peeling off the substrate, the gas barrier layer and the release resin layer The transfer method of the gas barrier film which transcribe | transfers a transfer layer provided to the said to-be-transferred body. The method for transferring a gas barrier film according to claim 13 , wherein the transfer target is any 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 laminated on the wavelength conversion layer, the wavelength conversion film having a transfer layer comprising the claims 1 was peeled off the substrate from the gas barrier film of any one of 12, the gas barrier layer and the peeling resin layer . Retardation film,
A gas barrier layer having the gas barrier layer according to any one of claims 1 to 12 laminated on the retardation film, and the transfer layer comprising the gas barrier layer and the peeling resin layer. Retardation film. An organic EL element,
The laminated on an organic EL, and peeling the substrate from the gas barrier film according to any one of claims 1 to 12 organic EL laminate having a transfer layer comprising a gas barrier layer and the release resin layer . The organic EL laminate according to claim 17 , further comprising a passivation film between the organic EL element and the transfer layer. Element substrate which supports the organic EL device, according to peel the substrate from the gas barrier film according to any one of claims 1 to 12, wherein the gas barrier layer and in the claims consists of the transfer layer comprising the release resin layer 17 Or the organic electroluminescent laminated body as described in 18 .