JP6399982B2 - Method for producing gas barrier film - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film using a transferable transfer gas barrier film, and a wavelength conversion film and an organic EL laminate using the gas barrier film produced by this production method.

In recent years, high gas barrier properties are required for devices such as organic EL devices (organic electroluminescence devices), solar cells, quantum dot films, and display materials, and packaging materials such as infusion bags that contain drugs that are altered by 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 such a gas barrier film, in order to use it in a field where high gas barrier properties are required, Patent Document 1 describes a configuration using an inorganic layer as a gas barrier layer or a multilayered gas barrier layer as a method for improving gas barrier properties. It describes that a gas barrier layer is formed on a resin film having a high glass transition temperature Tg.

Thus, the barrier film which has high gas barrier property is expand | deployed by various electronic devices and functional films, and makes it possible to seal the material which was difficult to seal conventionally.
For example, in Patent Document 2, as a quantum dot film used in a backlight unit such as an LCD, a quantum dot layer (QD phosphor material film layer) is sandwiched between two gas barrier films to protect the quantum dots. A stacked quantum dot film is described.
Patent Document 3 describes sealing an organic EL element using a gas barrier film.

As described above, by using a gas barrier film having a high gas barrier property, various electronic devices such as a display can be made thinner, lighter and more flexible. Therefore, if the gas barrier film can be made thinner, the electronic device can be made thinner and lighter.
As described in Patent Document 1 and the like, such a gas barrier film has a configuration in which a resin film is used as a substrate and a gas barrier layer is formed on the substrate. Therefore, in order to make the gas barrier film thinner, it is conceivable to make the substrate thinner.
Here, the gas barrier layer having a high gas barrier property is a thin inorganic layer, and cracks due to minute buckling or contact, resulting in a decrease in performance. Therefore, when laminating the gas barrier layer on a thin substrate, it is necessary to stabilize the conveyance so that the substrate can be prevented from buckling.

So, in patent document 4, by sticking a protective material on the back side of the substrate, the self-supporting property of the substrate can be secured, and even when a thin substrate is used, the substrate does not buckle, It describes that a gas barrier layer can be formed properly.
If such a method is used, a gas barrier layer can be formed even on a thin substrate of about a few tens of micrometers. However, if the thickness is smaller than this, it becomes difficult to attach the protective material for reinforcement while transporting the thin substrate.

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

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

US Pat. No. 5,565,084 Special table 2013-544018 gazette JP 2014-197537 A Japanese Patent Laying-Open No. 2015-66812 JP 2007-118564 A

Incidentally, electronic devices such as displays and functional films have been further increased in size, and a gas barrier film having a large area corresponding to this has been required.
However, when the area of the gas barrier film is increased, it is necessary to exhibit good gas barrier performance in the entire region, and quality assurance over the entire width and length becomes more difficult.
Moreover, in order to produce a gas barrier film that exhibits good gas barrier performance in the entire region, it becomes difficult to stabilize the production process, and it is difficult to produce the gas barrier film. Further, as the number of laminated layers is increased in order to improve the performance of the gas barrier film, the above-mentioned problem occurs by multiplication and the yield is further reduced. Therefore, it can be said that it is very difficult to produce a high-quality large-area gas barrier film. In addition, on the production equipment, the chamber of the vacuum film forming apparatus for forming the barrier layer becomes larger, and the time for one cycle such as exhaust and venting becomes longer, so the cost tends to increase.

  An object of the present invention is to solve such problems of the prior art, and a gas barrier film capable of easily and stably producing a large area gas barrier film that exhibits good gas barrier performance in all regions at low cost. And a wavelength conversion film and an organic EL laminate.

As a result of earnest research to achieve the above-mentioned problems, the present inventor has found that a gas barrier layer having one or more combinations of an inorganic layer and an organic layer on which the inorganic layer is formed on the substrate, and between the substrate and the gas barrier layer. A transfer film preparation step for preparing a transfer type gas barrier film provided on the substrate and having a release resin layer to be peeled from the substrate, and two or more transfer molds on the substrate to be transferred A first bonding step in which the gas barrier film is arranged in a plane direction and the gas barrier layer side is bonded to the substrate to be transferred, and a peeling step in which the substrate of the transfer type gas barrier film is peeled between the peeling resin layer and It has been found that the above problems can be solved by having the present invention, and the present invention has been completed.
That is, this invention provides the manufacturing method of the gas barrier film of the following structures, a wavelength conversion film, and an organic electroluminescent laminated body.

(1) Provided between the substrate and the gas barrier layer, the gas barrier layer having one or more combinations of the inorganic layer and the organic layer to be the formation surface of the inorganic layer, provided on one surface of the substrate, and organic A transfer film preparing step of preparing a transfer type gas barrier film having a release resin layer for adhering to the layer and peeling from the substrate;
A first laminating step in which two or more transfer-type gas barrier films are arranged in a plane direction on a substrate to be transferred, and the gas barrier layer side is bonded to the substrate to be transferred; and
A method for producing a gas barrier film, comprising a peeling step of peeling a transfer gas barrier film substrate from a release resin layer.
(2) The gas barrier film according to (1), which has an adhesive layer forming step of forming an adhesive layer on the gas barrier layer side of the transfer type gas barrier film or on the transferred substrate side before the first bonding step. Production method.
(3) Second bonding step in which a transfer type gas barrier film is further bonded onto the transfer layer including the gas barrier layer and the release resin layer that are bonded to the substrate to be transferred and peeled off after the peeling step. The manufacturing method of the gas barrier film as described in (1) or (2) which has these.
(4) In (3), the bonding position of the transfer type gas barrier film to be bonded in the second bonding process is different from the bonding position in the first bonding process in the surface direction of the transferred substrate. The manufacturing method of the gas barrier film of description.
(5) The distance between the end surfaces of the transfer layer provided with the gas barrier layer and the release resin layer, which are bonded to each other on the substrate to be transferred and peeled off, is 1 mm or less, or the width is 3 mm or less. The manufacturing method of the gas barrier film in any one of (1)-(4) which overlaps with.
(6) Refractive index adjustment that forms a refractive index adjustment layer on at least one of the surface of the substrate to be transferred opposite to the surface on which the transfer type gas barrier film is bonded and the release resin layer of the transfer type gas barrier film The manufacturing method of the gas barrier film in any one of (1)-(5) which has a layer formation process.
(7) Any of (1) to (6), wherein the refractive index adjusting layer is made of a mixture containing titanium, aluminum, zirconia, and fine particles made of at least one of these oxides, and acrylic or urethane. The manufacturing method of the gas barrier film of description.
(8) Formation of a light diffusion layer that forms a light diffusion layer on at least one of the surface of the substrate to be transferred opposite to the surface to which the transfer type gas barrier film is bonded and the release resin layer of the transfer type gas barrier film The manufacturing method of the gas barrier film in any one of (1)-(7) which has a process.
(9) The method for producing a gas barrier film according to any one of (1) to (8), wherein the light diffusing layer comprises particles serving as a diffusing material and a resin serving as a binder.
(10) The method for producing a gas barrier film according to any one of (1) to (9), wherein the water vapor permeability of the substrate to be transferred is less than 0.5 g / (m ² · day).
(11) The method for producing a gas barrier film according to any one of (1) to (10), wherein the substrate to be transferred is a retardation film.
(12) The method for producing a gas barrier film according to any one of (1) to (11), 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.
(13) The method for producing a gas barrier film according to (12), wherein the material for forming the release resin layer is a cycloolefin copolymer.
(14) An organic EL laminate having a gas barrier film produced by the method for producing a gas barrier film according to any one of (1) to (13).
(15) The organic EL laminate according to (14), wherein the transfer substrate is a retardation film.
(16) a wavelength conversion layer;
The wavelength conversion film which has a gas barrier film produced with the manufacturing method of the gas barrier film in any one of (1)-(13) laminated | stacked on the wavelength conversion layer.
(17) The light diffusing layer is provided on at least one of the surface of the substrate to be transferred opposite to the surface on which the transfer type gas barrier film is bonded and the release resin layer of the transfer type gas barrier film. Wavelength conversion film.

  According to the present invention, a method for producing a gas barrier film capable of easily and stably producing a large-area gas barrier film that exhibits good gas barrier performance in the entire region, a wavelength conversion film, and an organic EL A laminate can be provided.

1A is a side view conceptually showing an example of a gas barrier film produced by the production method of the present invention, and FIG. 1B is a top view of FIG. 1A. (C) is the elements on larger scale of FIG. 1 (A). FIG. 2 (A) is a side view conceptually showing another example of the gas barrier film produced by the production method of the present invention, and FIG. 2 (B) is a top view of FIG. 2 (A). FIG. 3A and FIG. 3B are diagrams conceptually illustrating an example of a transfer type gas barrier film. 4 (A) and 4 (B) are diagrams conceptually showing another example of the transfer type gas barrier film. FIG. 5 (A) to FIG. 5 (D) are conceptual diagrams for explaining an example of the method for producing a gas barrier film of the present invention. 6 (A) and 6 (B) are views showing an enlarged part of the gas barrier film of FIG. 1 (A). FIG. 7 (A) to FIG. 7 (D) are conceptual diagrams for explaining an example of the method for producing a gas barrier film of the present invention. FIG. 8 (A) and FIG. 8 (B) are conceptual diagrams for explaining the method for producing a gas barrier film of the present invention. FIGS. 9A and 9B are diagrams conceptually illustrating an example of a film forming apparatus for manufacturing a transfer type gas barrier film. It is sectional drawing which shows an example of an organic electroluminescent laminated body notionally. It is sectional drawing which shows an example of a wavelength conversion film notionally.

  Hereinafter, the manufacturing method of the gas barrier film of this invention is demonstrated in detail based on suitable embodiment shown by attached drawing.

The method for producing a gas barrier film of the present invention includes a substrate, a gas barrier layer having one or more combinations of an inorganic layer and an organic layer that forms an inorganic layer provided on one surface of the substrate, a substrate, and a gas barrier layer. A transfer film preparation step of preparing a transfer type gas barrier film provided between and having a release resin layer that is in close contact with the organic layer and is peeled from the substrate; A first gas bonding step in which a gas gas barrier film is arranged in a plane direction and the gas barrier layer side is bonded to a substrate to be transferred, and peeling is performed to peel the substrate of the transfer gas barrier film from the release resin layer. It is a manufacturing method of the gas barrier film which has a process.
The method for producing a gas barrier film of the present invention is to produce a gas barrier film having a large area by arranging and transferring a plurality of transfer-type gas barrier films on a substrate to be transferred.

First, FIG. 1 (A) to FIG. 1 (C) conceptually show an example of a gas barrier film produced by the method for producing a gas barrier film of the present invention (hereinafter also referred to as the production method of the present invention).
1A is a side view conceptually showing an example of a gas barrier film produced by the production method of the present invention, and FIG. 1B is a top view of FIG. 1A. (C) is the elements on larger scale of FIG. 1 (A).
A gas barrier film 100 shown in FIGS. 1A and 1B includes a substrate to be transferred 102, and a plurality of transfer layers 30 that are arranged and adhered to one surface of the substrate to be transferred 102 in the surface direction. Have The transfer layer 30 is a layer including a gas barrier layer 18 having a gas barrier property transferred from a transfer type gas barrier film 10 described later.

As shown in FIG. 1B, the transfer target substrate 102 of the gas barrier film 100 is a film-like member having a main surface of a square shape, and three sheets of transfer are formed on the main surface of the transfer substrate 102. Layers 30 are stacked side by side in the horizontal direction in the figure. That is, the length of the transfer layer 30 in the left-right direction is about 1/3 of the length of the transfer substrate 102 in the left-right direction. Further, as shown in the figure, the length of the transfer layer 30 and the length of the substrate to be transferred 102 are substantially the same in the vertical direction in the figure.
Thus, it can be set as a gas barrier film of a large area by having the some transfer layer 30 arranged in the surface direction and stuck on the to-be-transferred base material 102. FIG.

Here, as will be described in detail later, the transfer layer 30 is transferred to the transfer base 102 by peeling the substrate 12 after the transfer gas barrier film 10 is attached to the transfer base 102. is there.
Therefore, as shown in FIG. 1C, the gas barrier film 100 has an adhesive layer 24 on the substrate 102 to be transferred, and the gas barrier layer 18 including the inorganic layer 16 and the organic layer 14 on the adhesive layer 24. And has a release resin layer 20 on the organic layer 14. In the example shown in FIG. 1C, an adhesive layer 24 is formed on the inorganic layer 16 of the transfer type gas barrier film 10, and the transfer layer 30 of the transfer type gas barrier film 10 is transferred together with the adhesive layer 24. It is. Therefore, the gas barrier layer 18 and the release resin layer 20 including the adhesive layer 24 can also be referred to as the transfer layer 30.

In the example shown in FIG. 1A, the gas barrier film 100 is configured such that the three transfer layers 30 are arranged in the surface direction on the substrate 102 to be transferred. The transfer layer 30 may be arranged, or four or more transfer layers 30 may be arranged.
In the example shown in FIG. 1B, the gas barrier film 100 has a configuration in which a plurality of transfer layers 30 are arranged in one direction of the main surface of the substrate 102 to be transferred, but is not limited thereto. A configuration in which the transfer layer 30 is two-dimensionally arranged on the main surface of the transfer substrate 102 may be employed.

  In addition, the gas barrier film 100 shown in FIG. 1A has a configuration in which a plurality of transfer layers 30 are arranged in a plane direction on a substrate 102 to be transferred, that is, the transfer layer 30 in the thickness direction of the substrate 102 to be transferred. However, the present invention is not limited to this, and a structure in which a new transfer layer 30b is transferred onto the transfer layer 30, that is, a structure having two or more transfer layers in the thickness direction may be employed.

FIG. 2 (A) and FIG. 2 (B) conceptually show another example of a gas barrier film manufactured by the manufacturing method of the present invention.
FIG. 2 (A) is a side view conceptually showing an example of a gas barrier film produced by the production method of the present invention, and FIG. 2 (B) is a top view of FIG. 2 (A).
A gas barrier film 110 shown in FIGS. 2A and 2B includes a transfer target substrate 102, and a plurality of transfer layers 30 that are arranged and adhered to one surface of the transfer target substrate 102 in the surface direction. In addition, a plurality of transfer layers 30b arranged and adhered in a plane direction on the transfer layer 30 are provided.
The second transfer layer has the same configuration as that of the transfer layer 30 except that the arrangement position is different. For the sake of explanation, the second transfer layer is referred to as a transfer layer 30b.

As shown in FIG. 2 (B), the gas barrier film 110 is formed on the transfer layer 30 of the gas barrier film 100 shown in FIGS. 1 (A) and 1 (B). And a transfer layer 30b whose length in the left-right direction in the figure is half the length of the transfer layer 30 are arranged side by side in the left-right direction in the figure.
Thus, gas barrier properties can be further improved by laminating two or more transfer layers in the thickness direction.

In the example shown in FIG. 2A and FIG. 2B, as a preferable embodiment, the transfer layer 30 laminated on the transfer substrate 102 and the transfer layer 30b laminated on the transfer layer 30 are preferable. They are arranged at different positions in the plane direction.
That is, as shown in FIG. 2B, the transfer layer 30b is disposed so as to cover the boundary between the transfer layers 30, and the position of the boundary between the transfer layers 30b is the same as the position of the boundary between the transfer layers 30. Arranged so that they do not match.
Thereby, gas barrier property can be improved more.

  2B, the arrangement direction of the transfer layer 30 and the arrangement direction of the transfer layer 30b are aligned and laminated, but the present invention is not limited to this, and the arrangement direction of the transfer layer 30 is not limited thereto. And the arrangement direction of the transfer layer 30b may be different. For example, the arrangement direction of the transfer layer 30 b may be a direction orthogonal to the arrangement direction of the transfer layer 30.

Next, the transfer type gas barrier film used in the production method of the present invention will be described.
FIG. 3A conceptually shows an example of a transfer type gas barrier film.
3A is basically a substrate 12, 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, A release resin layer 20 is formed between the gas barrier layer 18 and the gas barrier layer 18.
As shown in FIG. 3A, the gas barrier layer 18 is laminated with the organic layer 14 facing the release resin layer 20 side, and the inorganic layer 16 is laminated on the organic layer 14. That is, the release resin layer 20 is laminated between the substrate 12 and the organic layer 14.

Here, as shown in FIG. 3B, in the transfer gas barrier film 10a, the release 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. Yes. That is, the peel force (adhesion force) between the organic layer 14 and the release resin layer 20 is greater than the peel force between the substrate 12 and the release resin layer 20.
Thereby, the transfer type 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-transferred base material 102 which is a sealing object. .

The transfer-type gas barrier film having such a structure is peeled at the interface between the release resin layer 20 and the substrate 12 when the substrate 12 is peeled off during transfer, so that the release gas barrier film exists between the inorganic layer 16 and the peeled surface. The resin layer 20 becomes a stress relaxation layer, and it is possible to prevent the inorganic layer 16 from being broken by the shearing force applied when the substrate 12 is peeled off.
Here, it is necessary to adjust the peeling force so that the peeling resin layer 20 peels at the interface with the substrate 12, and it is also necessary to have a function as a stress relaxation layer. Therefore, it is difficult to make it suitable as a base layer for the inorganic layer 16. In particular, in order to obtain the inorganic layer 16 having high gas barrier properties, the layer serving as the base of the inorganic layer 16 needs to have an 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. Cannot be formed, and high gas barrier properties cannot be obtained.

On the other hand, since the above-mentioned transfer type gas barrier film has the organic layer 14 on the peeling 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 formed appropriately and high gas barrier properties can be obtained.
Therefore, the manufacturing method of this invention can transfer suitably the transfer layer 30 which has high gas barrier property by using such a transfer type gas barrier film.

Here, the structure of the transfer type gas barrier film is not limited to the example shown in FIG. 3A, and may further include other layers.
For example, it is good also as a structure which has the adhesion layer 24 on the gas barrier layer 18 (inorganic layer 16) like the transfer type gas barrier film 10b shown to FIG. 4 (A).
Since the adhesive layer 24 has adhesiveness, the transfer layer 30 can be easily transferred without applying an adhesive or the like when the transfer layer 30 is transferred to the transfer target, and the adhesive layer 24 is provided. Thus, it is possible to prevent the inorganic layer 16 from being broken when the transfer type gas barrier film is conveyed or wound.
When the adhesive layer 24 is provided, the release resin layer 20, the gas barrier layer 18, and the adhesive layer 24 become the transfer layer 30, and the adhesive layer 24 is transferred to the transfer object together with the release resin layer 20 and the gas barrier layer 18. .

  In addition, as shown in FIG. 4A, when the adhesive layer 24 is provided, it is preferable to have a protective film 26 on the adhesive layer 24. By having the protective film 26, the transfer type gas barrier film can be easily transported and wound, and dust or the like can be prevented from adhering to the adhesive layer or the adhesiveness can be prevented from being lowered.

In the example shown in FIG. 3A, the gas barrier layer 18 includes one organic layer 14 and one inorganic layer 16. However, the present invention is not limited to this, and the organic layer and the inorganic layer are not limited thereto. Each of them may have one or more layers, and may have two or more combinations of the inorganic layer 16 and the organic layer 14 which is the base layer of the inorganic layer 16.
For example, a transfer type gas barrier film 10c shown in FIG. 4B has a gas barrier layer 18 in which an organic layer 14, an inorganic layer 16, an organic layer 14, and an inorganic layer 16 are formed in this order on a release resin layer 20. That is, the gas barrier layer 18 of the transfer type gas barrier film 10c has a configuration having two combinations of the organic layer 14 and the inorganic layer 16.
Thus, by having two or more combinations of the organic layer 14 and the inorganic layer 16, the gas barrier property can be further improved.

Here, in the transfer-type gas barrier film having the above-described configuration, the water vapor permeability of the transfer layer 30 including the gas barrier layer 18 and the release resin layer 20 from which the substrate 12 has been peeled is 0.01 [g / (m ² · day)], preferably 0.005 [g / (m ² · day)] or less, particularly preferably 0.001 [g / (m ² · day)] or less. preferable.
The transfer type gas barrier film described above has a low water vapor transmission rate, that is, even the transfer layer 30 having a high gas barrier property prevents cracking of the inorganic layer 16 and the like, while maintaining a high gas barrier property. Can be transferred appropriately.

  Next, materials and configurations of each component of the gas barrier film and the transfer type gas barrier film will be described.

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

  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), polyacrylonitrile (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 preferably exemplified.

  In the present invention, necessary functions such as a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, a stress relaxation layer, and a release layer are provided on the surface of such a film. A substrate in which a layer (film) that expresses a film is formed may be used as the substrate 12.

  Among these, from the viewpoints of high elongation at break and difficulty in breaking during transportation, the substrate 12 can be made thinner, has a high melting point and heat resistance, can be easily peeled at the interface with the release resin layer 20, and is inexpensive. As, as for the thing in which the mold release layer was formed in the surface in which the peeling resin layer 20 of PET film is formed.

What is necessary is just to set the thickness of the board | substrate 12 suitably according to the use, forming material, etc. of the transfer type gas barrier film 10. FIG.
According to the study 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, it is preferable in that the mechanical strength of the transfer type gas barrier film 10 can be sufficiently secured and peeling can be easily performed at the time of transfer.

  The organic layer 14 is a layer made of an organic compound, and is basically obtained by polymerizing (crosslinking) a monomer, an oligomer, or the like that becomes the organic layer 14.

The organic layer 14 functions as a base layer for appropriately forming the inorganic layer 16 that mainly exhibits gas barrier properties in the transfer type gas barrier film 10.
By having such an organic layer 14, the surface of the release resin layer 20 (or the lower inorganic layer 16) is embedded in the surface of the release resin layer 20. The film formation surface 16 can be in a state suitable for the film formation of the inorganic layer 16. This eliminates areas where the inorganic compound that becomes the inorganic layer 16 is difficult to deposit, such as unevenness on the surface of the substrate 12 and unevenness due to adhesion of foreign matter, and the appropriate inorganic layer 16 without gaps on the entire surface of the substrate. Thus, the inorganic layer 16 having a high gas barrier property can be formed.

Moreover, it is preferable that the glass transition temperature Tg of the organic layer 14 is higher than the glass transition temperature Tg of the peeling resin layer 20, and it is preferable that it is 200 degreeC or more.
By forming the organic layer 14 having a high heat resistance with a glass transition temperature Tg of 200 ° C. or higher, the inorganic layer 16 can be appropriately formed.
The organic layer 14 preferably has appropriate flexibility in order to prevent the inorganic layer 16 from cracking.
In the present invention, the glass transition temperature Tg may be measured according to JIS K7121.

In the transfer gas barrier film 10, the material for forming the organic layer 14 is not limited, and various known organic compounds can be used.
Specifically, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, poly Ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acrylic compounds, thermoplastic resins, polysiloxane and other An organic silicon compound film is preferably exemplified. A plurality of these may be used in combination.

Among them, the organic layer 14 composed of a polymer of a radical curable compound and / or a cationic curable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.
Among these, acrylic resins and methacrylic resins mainly composed of acrylate and / or methacrylate monomers and oligomer polymers are suitable as the organic layer 14 in terms of low refractive index, high transparency, and excellent optical properties. Is exemplified.
Among them, in particular, dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. Acrylic resins and methacrylic resins mainly composed of polymers such as acrylate and / or methacrylate monomers and oligomers are preferably exemplified. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.

Here, the material for forming the organic layer 14 is preferably an ultraviolet curable resin or an electron beam curable resin.
By using an ultraviolet curable resin or an electron beam curable resin as a material for forming the organic layer 14, the peeling force with the release resin layer 20 can be easily adjusted by the irradiation amount of the ultraviolet ray or the electron beam. Can be realized. Therefore, it can be set as the structure peeled 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% monofunctional or higher acrylate having an adamantane skeleton, or 5% or more and less than 50% bifunctional or higher acrylate having a fluorene skeleton. The resin material is preferably included.
By using a resin material containing a monofunctional or higher acrylate having an adamantane skeleton or a bifunctional or higher acrylate having a fluorene skeleton as a material for forming 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 cracking.

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

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 applied onto the release resin layer 20. The organic layer 14 can be formed by forming a coating film and drying and curing the coating film.
The organic layer 14 can be formed thin by forming it by a coating method.

  As described above, when a plurality of organic layers 14 are provided, the thickness of each organic layer 14 may be the same or different from each other. 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 transfer type gas barrier film 10, the target gas barrier property is mainly expressed by the inorganic layer 16.

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

  Such an inorganic layer 16 is formed by CCP-CVD (capacitively coupled plasma enhanced chemical vapor deposition) or ICP-CVD (inductively coupled plasma enhanced chemical vapor deposition) depending on the material for forming the inorganic layer 16. , Sputtering, vacuum deposition or the like may be performed by a known vapor deposition method.

The thickness of the inorganic layer 16 may be determined as appropriate according to the forming material so that the target gas barrier property can be exhibited. According to the study 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 expresses 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 of causing cracks, cracks, peeling, etc. However, if the thickness of the inorganic layer 16 is 200 nm or less, cracks will occur. Can be prevented.

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

In the transfer gas barrier film 10, a release resin layer 20 is provided between the substrate 12 and the organic layer 14.
As described above, the release resin layer 20 is a resin layer that is in close contact with the organic layer 14 and can be peeled off from the substrate 12 at the interface with the substrate 12, and is sheared onto the inorganic layer 16 when the substrate 12 is peeled off. This layer also functions as a stress relaxation layer that suppresses the application of force. Further, after the substrate 12 is peeled, the release resin layer 20 also functions as a support.

Here, the release resin layer 20 preferably has low water content and high heat resistance.
As described above, the inorganic layer 16 that exhibits high gas barrier properties needs to be formed by vacuum film formation such as plasma CVD. When the moisture content of the release resin layer 20 is high, moisture is released even if evacuation is performed, so that the degree of vacuum cannot be increased and the inorganic layer 16 may not be formed. Even when the inorganic layer 16 is formed, if the release resin layer 20 expands and contracts due to absorption and release of moisture, the inorganic layer 16 may break and high gas barrier properties may not be obtained. Therefore, it is preferable that the release resin layer 20 has a low water content. Moreover, since the inorganic layer 16 is formed by plasma CVD etc., it is preferable that heat resistance is high.

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

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

The release resin layer 20 can be formed by a coating method similar to that for the organic layer 14.
The release resin layer 20 can be formed thin by forming by a coating method.

The thickness of the release resin layer 20 may be appropriately set according to the material for forming the release resin layer 20, the organic layer 14, the inorganic layer 16, and the substrate 12. According to the study by the present inventors, the thickness of the release resin layer 20 is preferably 0.1 to 25 μm, more preferably 0.5 to 15 μm, and particularly preferably 1 to 10 μm. preferable.
By setting the thickness of the release 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. The shearing force applied to the inorganic layer 16 when the substrate 12 is peeled can be reduced to prevent the inorganic layer 16 from cracking.
Further, by setting the thickness of the release resin layer 20 to 25 μm or less, occurrence of problems such as cracks in the release resin layer 20 and curling of the transfer type gas barrier film 10 due to the release resin layer 20 being too thick, It can suppress suitably, and can make it easy to wind up the transfer type gas barrier film 10 in roll shape.

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

Here, the release resin layer 20 is preferably thicker than the organic layer 14.
As described above, the organic layer 14 serving as the base layer of the inorganic layer 16 needs higher heat resistance. Therefore, it is necessary to use a material having a higher glass transition temperature Tg as a material for forming the organic layer 14. Here, in general, a material having a high glass transition temperature Tg is hard and difficult to stretch. Therefore, by reducing the thickness of the hard organic layer 14 and increasing the thickness of the soft release resin layer 20, the release resin is obtained. The layer 20 can function properly as a stress relaxation layer, and cracking of the inorganic layer 16 when the substrate 12 is peeled can be prevented to obtain high gas barrier properties.

Further, the peeling force between the release 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.
Further, the peeling force between the release resin layer 20 and the substrate 12 is preferably 0.04 N / 25 mm to 1 N / 25 mm.
By setting the peeling force between the release resin layer 20 and the substrate 12 in the above range, the peeling force is too weak and can be prevented from being peeled off during transportation or the like, and the peeling force is too strong. It is possible to suppress inconveniences such as damage to the inorganic layer 16 during peeling and deformation of the transfer gas barrier film 10.
In addition, what is necessary is just to measure peeling force (adhesion force) according to the 180 degree peeling test method of JISZ0237.

The adhesive layer 24 is a layer made of an organic compound and is formed on the gas barrier layer 18 (inorganic layer 16). When the transfer layer 30 is transferred to the transfer substrate 102, the transfer layer 30 and the transfer substrate 102 It is for sticking.
There are no limitations on the material for forming the adhesive layer 24 as the adhesive layer, and various known adhesive materials can be used.
From the viewpoint of optical properties, particularly retardation and haze, it is preferable to use an acrylic pressure-sensitive adhesive as the pressure-sensitive adhesive material.
Examples of the acrylic pressure-sensitive adhesive include SK Dyne series (manufactured by Soken Chemical Co., Ltd.).

The thickness of the adhesive layer 24 may be appropriately set according to the material for forming the adhesive layer 24 and the inorganic layer 16. According to the study by the present inventors, the thickness of the adhesive layer 24 is preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm, and particularly preferably 1 to 10 μm. .
By setting the thickness of the adhesive layer 24 to 0.1 μm or more, the inorganic layer 16 can be appropriately protected. Moreover, the workability | operativity at the time of sticking the transfer type gas barrier film 10 to a to-be-transferred body can be improved because the thickness of the adhesion layer 24 shall be 50 micrometers or less.

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

Here, the material for forming 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 that is the uppermost layer of the gas barrier layer 18 of the transfer gas barrier film 10, and is used by being peeled from the inorganic layer 16 when transferring the transfer gas barrier film 10. The By setting the Young's modulus of the forming material of the protective film 26 to 6 GPa or less, damage to the inorganic layer 16 when the protective film 26 is peeled can be more suitably prevented, and high gas barrier properties can be obtained.
Considering this point, LDPE, HDPE, PP, PET, PEN, PVC, PI and the like are preferably exemplified as the forming material of the protective film 26.

What is necessary is just to set the thickness of the protective film 26 suitably according to the thickness requested | required of the transfer type gas barrier film 10, the Young's modulus of the forming material of the protective film 26, etc.
According to the study by 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 impact received from the outside during winding, etc., and to prevent wrinkles and deformation during transportation. Is preferable.
Setting the thickness of the protective film 26 to 300 μm or less is preferable in that the transfer type gas barrier film 10 can be prevented from becoming unnecessarily thick.

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

The transferred substrate 102 is a substrate that supports the transfer layer 30 transferred from the transfer gas barrier film 10 in a state of being arranged in the surface direction.
As the transfer substrate 102, various known sheet-like materials that are used as known substrates can be used.
As an example, the film (resin film) which consists of various resin materials illustrated with the above-mentioned board | substrate 12 is illustrated suitably.
Among these, TAC, PC, COC, and COP are preferably used from the viewpoint of optical characteristics, particularly retardation, and PET is preferable from the viewpoint of transportability and thinning.

Here, it is preferable that the water vapor transmission rate of the substrate to be transferred 102 is less than 0.5 g / (m ² · day).
By using a substrate having a low water vapor transmission rate as the transferred substrate 102, the gas barrier property can be maintained even if there is a minute gap between the transfer layers 30 arranged on the transferred substrate 102.

Next, the manufacturing method of the gas barrier film of this invention is demonstrated.
The method for producing a gas barrier film of the present invention is a method for producing the above gas barrier film, wherein one or more combinations of a substrate and an inorganic layer provided on one surface of the substrate and an organic layer forming the inorganic layer are provided. A transfer film preparatory step for preparing a transfer type gas barrier film having a gas barrier layer having a release resin layer provided between the substrate and the gas barrier layer, in close contact with the organic layer, and for peeling from the substrate;
A first laminating step in which two or more transfer-type gas barrier films are arranged in a plane direction on a substrate to be transferred, and the gas barrier layer side is bonded to the substrate to be transferred; and
It is a manufacturing method of the gas barrier film which has the peeling process which peels the board | substrate of a transfer type gas barrier film between peeling resin layers.
Hereinafter, the manufacturing method of this invention is demonstrated using FIG. 5 (A)-FIG. 5 (D).

  FIGS. 5A to 5D show an example in which a gas barrier film 100 as shown in FIG. 1A is manufactured by transferring three transfer-type gas barrier films to the substrate 102 to be transferred. It is shown.

First, in the transfer film preparation step, for example, a transfer type gas barrier film 10b as shown in FIG. 4A is prepared. As described above, the transfer type gas barrier film 10a shown in FIG. 4A includes the substrate 12, the gas barrier layer 18 having the organic layer 14 and the inorganic layer 16 laminated on one surface of the substrate 12, the substrate 12, This is a laminate having a release resin layer 20 laminated between the gas barrier layer 18, an adhesive layer 24 laminated on the gas barrier layer 18 (inorganic layer 16), and a protective film 26 protecting the adhesive layer 24. .
A method for producing such a transfer type gas barrier film will be described in detail later.

Next, in the first bonding step, as shown in FIG. 5A, a plurality of prepared transfer-type gas barrier films 10 are aligned and bonded onto the transfer substrate 102 in the surface direction.
At that time, as shown in FIG. 5B, the end faces of the transfer gas barrier film 10 are arranged in close contact with each other.
There is no limitation in the bonding method in a 1st bonding process, The bonding method of a various well-known film-form thing can be utilized.

  Here, when the transfer type gas barrier film 10b having the adhesive layer 24 and the protective film 26 as described above is used as the transfer type gas barrier film, before the transfer type gas barrier film 10b is bonded to the substrate 102 to be transferred, After the protective film 26 is peeled off and the adhesive layer 24 is exposed, it may be bonded.

Next, in the peeling step, as shown in FIG. 5C, the substrate 12 is peeled from the transfer type gas barrier film 10 stuck on the transfer base material 102.
There is no limitation in the peeling method of the board | substrate 12 in a peeling process, The peeling method of a various well-known film-like thing can be utilized.
As described above, the transfer-type gas barrier film 10 has the release resin layer 20 between the substrate 12 and the gas barrier layer 18 and is peeled between the substrate 12 and the release resin layer 20. When the film is peeled off, the transfer layer 30 including the gas barrier layer 18 and the release resin layer 20 is left on the substrate 102 to be transferred, and the gas barrier film 100 as shown in FIG.

As described above, electronic devices such as displays and functional films are further increased in size, and a gas barrier film having a large area corresponding to this has been required.
However, when the area of the gas barrier film is increased, it is necessary to exhibit good gas barrier performance in the entire region, and quality assurance over the entire width and length becomes more difficult.
Moreover, in order to produce a gas barrier film that exhibits good gas barrier performance in the entire region, it becomes difficult to stabilize the production process, and it is difficult to produce the gas barrier film. Further, as the number of laminated layers is increased in order to improve the performance of the gas barrier film, the above-mentioned problem occurs by multiplication and the yield is further reduced. Therefore, it can be said that it is very difficult to produce a high-quality large-area gas barrier film. In addition, on the production equipment, the chamber of the vacuum film forming apparatus for forming the barrier layer becomes larger, and the time for one cycle such as exhaust and venting becomes longer, so the cost tends to increase.

On the other hand, in the production method of the present invention, two or more transfer-type gas barrier films 10 are arranged and transferred in the surface direction of the substrate 102 to be transferred, thereby producing a gas barrier film having a larger area than one transfer-type gas barrier film. .
Here, as described above, the transfer type gas barrier film 10 used in the present invention is configured such that the release resin layer 20 is in close contact with the organic layer 14 of the gas barrier layer 18 and can be peeled off from the substrate 12 at the interface with the substrate 12. ing. As a result, when the substrate 12 is peeled off at the time of transfer, the peeling resin layer 20 existing between the inorganic layer 16 and the peeling surface becomes a stress relaxation layer by peeling at the interface between the peeling resin layer 20 and the substrate 12. The inorganic layer 16 can be prevented from being broken by the shearing force applied when the substrate 12 is peeled off, and the transfer layer 30 after transfer can also exhibit high gas barrier properties.
Therefore, the transfer type gas barrier film 10 can be transferred while maintaining a high gas barrier property, and a gas barrier film having a high gas barrier property and a large area can be easily and stably produced at a low cost.

  Here, in the manufacturing method of the present invention, since the transfer gas barrier film 10 having the substrate 12 is bonded to the transfer base material 102 in the first bonding step, the substrate 12 is peeled off. At the time of alignment, the end surfaces of the transfer gas barrier film 10 having the substrate 12 in a thick state are attached to each other and bonded together, so that the arrangement interval of the thin transfer layers 30 can be arranged very small.

  In the above-described example, the substrate 12 of the transfer gas barrier film 10 is peeled after all the transfer gas barrier film 10 is bonded to the transfer base material 102. However, the present invention is not limited to this. Bonding and peeling of the substrate 12 may be performed for each transfer gas barrier film 10.

In addition, the transfer layer 30 transferred to the transfer target substrate 102 may have a gap between the adjacent transfer layer 30 and the end face, or may overlap.
In the manufacturing method of the present invention, the transfer gas barrier film 10 is used to transfer the thin transfer layer 30. Therefore, compared to a configuration in which a plurality of ordinary gas barrier films are arranged and bonded, the transfer layer 30 is interposed between the transfer layers 30. Even when there is a gap, the step with the gap can be made very small, and even when the transfer layers 30 overlap each other, the overlapping step can be made very small, and the boundary of the transfer layer 30 can be visually recognized as a streak. Can be suppressed.
The configuration in which the adjacent transfer layers 30 overlap is more preferable from the viewpoint of gas barrier properties and the like, and the configuration in which the adjacent transfer layers 30 have gaps is more preferable from the viewpoint of flatness and the like.
As shown in FIG. 6A, when a gap t1 is present between adjacent transfer layers 30, the gap t1 is preferably 1 mm or less, and more preferably 0.3 mm or less.
As shown in FIG. 6B, when adjacent transfer layers 30 overlap each other, the overlap t2 is preferably 3 mm or less, and more preferably 1 to 3 mm.

In the above-described example, the transfer type gas barrier film 10 has an adhesive layer. However, the present invention is not limited to this, and the adhesive layer adheres to the transferred substrate 102 before being bonded to the transferred substrate 102. An agent may be applied and bonded to the transfer gas barrier film 10.
That is, the above-mentioned example is a configuration including an adhesive layer forming step in the step of preparing the transfer type gas barrier film (preparation step), but the adhesive layer is applied to the substrate to be transferred 102 before the first bonding step. The structure which has the adhesion layer formation process to form may be sufficient.

  Moreover, the 1st bonding process and peeling process which were mentioned above may be performed by a sheet style, and may be performed by RtoR.

  The manufacturing method of the present invention further includes a second bonding step of bonding a transfer type gas barrier film onto the transfer layer 30 transferred to the transfer substrate 102, and the transfer layer in the thickness direction. Two or more layers of the gas barrier film 110 as shown in FIG.

That is, as shown in FIG. 7A, in the second bonding step, the transfer type gas barrier film 10 is bonded onto the transfer layer 30 transferred to the transfer substrate 102 after the peeling step.
Here, as shown in FIG. 7B, the bonding position of the transfer type gas barrier film 10 bonded in the second bonding step is the bonding of the transfer layer 30 bonded in the first bonding step. The position is preferably different from the alignment position. That is, as described above, the transfer-type gas barrier film 10 having the transfer layer 30b is bonded so as to cover the boundary between the transfer layers 30, and the boundary between the transfer layers 30b bonded in the second bonding step. The bonding is performed so that the position does not coincide with the position of the boundary between the transfer layers 30.
There is no limitation also in the bonding method in a 2nd bonding process, The bonding method of a various well-known film-form thing can be utilized.

Next, as shown in FIG. 7C, the substrate 12 of the transfer type gas barrier film 10 bonded in the second bonding step is peeled off as the second peeling step.
There is no limitation on the method of peeling the substrate 12 in the second peeling step, and various known film-like peeling methods can be used.
When the substrate 12 is peeled off, the transfer layer 30b is left on the transfer layer 30, and a gas barrier film 110 as shown in FIG.

  Thus, gas barrier properties can be further improved by laminating two or more transfer layers in the thickness direction. In particular, as shown in FIG. 6A, when there is a gap between the transferred transfer layers 30, the gap can be sealed to further improve the gas barrier property, and the flatness of the gas barrier film can also be improved. .

Moreover, the manufacturing method of this invention may have the process (refractive index adjustment layer formation process, light diffusion layer formation process) of forming optical function layers, such as a refractive index adjustment layer and a light-diffusion layer, further.
At that time, as shown in FIG. 8A, the optical functional layer 104 such as a refractive index adjusting layer or a light diffusing layer is a surface on the opposite side of the surface of the substrate 12 to which the transfer layer 30 is transferred. Alternatively, it may be formed on the transferred transfer layer 30 as shown in FIG.

The refractive index adjustment layer adjusts the refractive index of the surface of the gas barrier film 100 and suppresses reflection of light at the gas barrier film 100 and the air interface so that the boundary of the transfer layer 30 of the gas barrier film 100 is more visible. It is for preventing suitably.
The material for forming the refractive index adjustment layer is not limited, and various known materials that are used as the refractive index adjustment layer can be used.
For example, as a material for forming the refractive index adjustment layer, a material composed of a mixture containing titanium, aluminum, zirconia and fine particles composed of at least one of these oxides and an acrylic or urethane resin as a binder is preferably used. Is possible.

The light diffusion layer is for diffusing light transmitted through the gas barrier film 100.
The material for forming the light diffusion layer is not limited, and various known materials that are used as the light diffusion layer can be used.
As an example, as a material for forming the light diffusion layer, a material composed of particles serving as a diffusion material and a resin serving as a binder can be suitably used.
Examples of the diffusing material include silicone particles, PMMA particles, and PMMB particles.
Moreover, as a binder, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane, Polyetheretherketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acrylic compounds, thermoplastic resins, polysiloxane, and others Examples of the resin such as organosilicon compound are given below.

  By having the light diffusion layer, it is possible to more suitably prevent the boundary of the transfer layer 30 of the gas barrier film 100 from being visually recognized.

  Moreover, you may have two or more optical function layers, such as a refractive index adjustment layer and a light-diffusion layer. For example, the gas barrier film may have a configuration having two refractive index adjustment layers, or may have a configuration having a refractive index adjustment layer and a light diffusion layer. In that case, two layers may be laminated | stacked on the same surface side, and may be laminated | stacked on the other surface side mutually.

Hereinafter, with reference to FIG. 9 (A) and FIG. 9 (B), the manufacturing method of a transfer type gas barrier film is demonstrated.
In the following example, as a preferred embodiment, a transfer type gas barrier film is produced by RtoR using the long substrate 12, the protective film 26, and the like. As is well known, RtoR means that a processed object is sent out from a roll formed by winding a long processed object, and is subjected to processing such as film formation while being conveyed in the longitudinal direction. This is a manufacturing method in which the material is wound again in a roll shape.

First, the release resin layer 20 is formed over the substrate 12 using a film formation apparatus conceptually illustrated in FIG.
Specifically, a coating composition containing an organic solvent, an organic compound that becomes the release resin layer 20, and the like is prepared.
On the other hand, a substrate roll Ra obtained by winding a long substrate 12 into a roll is loaded into a predetermined position of the organic film forming apparatus shown in FIG. Next, the substrate 12 is sent out from the substrate roll Ra and passed through a predetermined path to the winding position. Further, the prepared coating composition to be the release resin layer 20 is filled in a predetermined position of the coating unit 40. Note that reference numerals 48 and 49 in the drawing denote a pair of transport rollers for transporting the substrate 12 along a predetermined path.
Then, the substrate 12 is fed out from the substrate roll Ra, and while being transported in the longitudinal direction, 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. Further, if necessary, the cured resin 44 is irradiated with ultraviolet rays or heated to form the release resin layer 20. Further, a long film in which the release resin layer 20 is formed on the substrate 12 is wound into a roll to obtain a base roll Rb.
In addition, as shown to a figure, after forming the peeling resin layer 20, as a preferable aspect, the protective film 28 is laminated | stacked from the protective film roll 28R, and it winds up after that, and is set as the base material roll Rb. The protective film 28 is the same as the protective film 26 described above.

Next, the substrate 12 on which the release resin layer 20 is formed is used as the film formation substrate Za, and the organic layer 14 is formed on the release resin layer 20 of the film formation substrate Za. The formation of the organic layer 14 may be basically performed in the same manner as the formation of the release resin layer 20 using an organic film forming apparatus as shown in FIG.
That is, a coating composition containing an organic solvent, an organic compound that becomes the organic layer 14, a polymerization initiator, and the like is prepared.
Further, a base material roll Rb obtained by winding a long film formation base material Za into a roll shape is loaded into a predetermined position of the organic film forming apparatus shown in FIG. Next, the deposition target substrate Za is sent out from the substrate roll Rb, and is passed through a predetermined path to the winding position. Furthermore, the coating composition which becomes the prepared organic layer 14 is filled into a predetermined position of the coating unit 40.
Then, the film-forming substrate Za is sent out 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. Then, the coating composition is dried, and the organic layer 14 is formed by polymerizing (crosslinking) the organic compound in the cured portion 44 by ultraviolet irradiation or the like. Further, the long film-forming substrate Za on which the organic layer 14 is formed is wound into a roll shape to form a substrate roll Rc.

As in the case of the release resin layer 20, a protective film 28 may be attached to the organic layer 14 after the organic layer 14 is formed. The protective film 28 is preferably attached before the organic layer 14 contacts another member such as a guide roller.
Thereby, it is possible to prevent the organic layer 14 that is the base layer of the inorganic layer 16 from being damaged, and the inorganic layer 16 can be appropriately formed on the smooth organic layer 14, thereby obtaining a gas barrier film that exhibits high gas barrier properties. Can do.
In the above example, the film formation of the release resin layer 20 and the film formation of the organic layer 14 are performed. However, the present invention is not limited to this, and winding is not performed after the film formation of the release resin layer. Subsequently, the organic layer 14 may be formed. That is, in the conveyance path of the substrate 12, a coating unit 40, a drying unit 42 and a curing unit 44 for forming the release resin layer 20, and a coating unit 40, a drying unit 42 and curing for forming the organic layer 14. Using the film forming apparatus in which the portion 44 is disposed, the film formation of the release resin layer 20 and the film formation of the organic layer 14 may be performed continuously.

Next, in an inorganic film forming apparatus conceptually shown in FIG. 9B, the inorganic layer 16 is formed on the substrate 12 (deposition substrate Zb) on which the release resin layer 20 and the organic layer 14 are formed, and The protective film 29 is stuck to the inorganic layer 16.
The inorganic film forming apparatus shown in FIG. 9B forms the inorganic layer 16 by CCP-CVD (capacitive coupling type plasma chemical vapor deposition method) as an example, and includes a supply chamber 50 and a film forming chamber 52. And a winding chamber 54.
First, the base roll Rc is loaded at a predetermined position in the supply chamber 50. Next, the deposition target substrate Zb is sent out from the substrate roll Rc, and the paper passes through a predetermined path from the supply chamber 50 to the winding chamber 54 through the deposition chamber 52. The base material roll Rc is loaded so that the organic layer 14 becomes a film formation surface in the film formation chamber 52.
Further, the protective film roll 29R is loaded at a predetermined position in the film forming chamber 52. Next, the protective film 29 is sent out from the protective film roll 29 </ b> R, and the paper passes through a predetermined path from the film formation chamber 52 to the winding chamber 54.

Next, the supply chamber 50 is evacuated by the vacuum evacuation means 50a, the film formation chamber 52 is evacuated by the vacuum evacuation means 52a, and the winding chamber 54 is evacuated by the vacuum evacuation means 54a.
When the pressure in each chamber reaches a predetermined pressure, conveyance of the film formation substrate Zb and the protective film 29 is started.

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

On the other hand, in synchronization with the transport of the film-forming substrate Zb, the protective film 29 is sent out from the protective film roll 29R and transported in the longitudinal direction.
The deposition target substrate Zb and the protective film 29 on which the inorganic layer 16 is formed are laminated and pressure-bonded by the lamination roller pair 72, and the transfer type gas barrier film 10 is produced.
An adhesive layer may be formed on the surface of the protective film 29 that faces the inorganic layer 16.

When producing the transfer type gas barrier film 10 by RtoR, it is preferable that the protective film 29 is attached after the inorganic layer 16 is formed and before the inorganic layer 16 comes into contact with another member such as a guide roller. .
Thereby, the transfer type gas barrier film 10 which prevents the damage of the inorganic layer 16 and expresses the target gas barrier property is obtained.

  In the film forming chamber 52, the transfer type gas barrier film 10 produced by laminating and sticking the laminated film and the protective film 26 by the laminated roller pair 72 is conveyed from the film forming chamber 52 to the take-up chamber 54 and is guided by the guide roller. The barrier film roll Rd is wound around the long transfer-type gas barrier film 10 by being guided by a predetermined path 76 and wound up.

In the case where the film-forming substrate Zb has the protective film 28 on the organic layer 14, the protective film is peeled off to form the inorganic layer 16 before the inorganic layer 16 is formed. Just do it.
The protective film is preferably peeled off at a position where there is no member such as a guide roller in contact with the organic layer 14 in the path to the film forming means for the inorganic layer 16.

  When the adhesive layer 24 is further formed on the inorganic layer 16, the substrate 12 on which the release resin layer 20, the organic layer 14, and the inorganic layer 16 are formed is used as a film formation base material Zc. The adhesive layer 24 may be formed in the same manner as the release resin layer 20 and the organic layer 14 using an organic film forming apparatus as shown in FIG.

That is, a base material roll Rd obtained by winding a long film formation base material Zc in a roll shape is loaded into a predetermined position of the organic film forming apparatus shown in FIG. Next, the deposition target substrate Zc is sent out from the substrate roll Rd, and is passed through a predetermined path to the winding position. Further, the prepared coating composition to be the adhesive layer 24 is filled in a predetermined position of the coating unit 40.
Further, the protective film roll 26R is loaded at a predetermined position of the organic film forming apparatus. Next, the protective film 26 is sent out from the protective film roll 26 </ b> R and passed through a predetermined path reaching the conveying roller pair 49.

Then, the film-forming substrate Zc is sent out from the substrate roll Rd, and the coating composition prepared in the coating unit 40 is coated on the inorganic layer 16 while being transported in the longitudinal direction. In addition, although illustration is abbreviate | omitted, the protective film 29 is peeled before application | coating of a coating composition.
Next, the coating composition is dried in the drying unit 42, and the organic compound is cured by ultraviolet irradiation or the like in the curing unit 44 as necessary to form the adhesive layer 24.
On the other hand, the protective film 26 is sent out from the protective film roll 26R and conveyed in the longitudinal direction in synchronization with the conveyance of the film formation substrate Za.
The film-forming substrate Zc and the protective film 26 on which the adhesive layer 24 is formed are laminated and pressure-bonded by the conveying roller pair 49 to produce the transfer type gas barrier film 10b.

  Hereinafter, the member using the gas barrier film manufactured with the manufacturing method of this invention is demonstrated.

  FIG. 10 is an example of an organic EL laminate in which an organic EL element is sealed using a gas barrier film produced by the production method of the present invention.

An organic EL laminate 120 shown in FIG. 10 includes a gas barrier film 100, an organic EL element 124 formed on the gas barrier film 100, an adhesive layer 126 and a gas barrier film 100 laminated so as to cover the organic EL element 124.
That is, the organic EL laminate 120 in the illustrated example uses the gas barrier film 100 as an element substrate for forming the organic EL element 124 and also uses the gas barrier film 100 as a sealing film for sealing the organic EL element 124. It was.

The organic EL element 124 is a known organic EL element having, for example, an organic electroluminescent layer and a transparent electrode and a reflective electrode that are an electrode pair that holds the organic electroluminescent layer.
As shown in the figure, the organic EL element 124 is sealed while being sandwiched by the gas barrier film 100 manufactured by the manufacturing method of the present invention.
Thus, the organic EL laminated body can be enlarged by sealing the organic EL element 124 with the gas barrier film manufactured by the manufacturing method of the present invention.

In the illustrated example, the organic EL laminate uses the gas barrier film produced by the production method of the present invention as the element substrate and the sealing film. However, the present invention is not limited to this, and the element substrate or the sealing film is used. It is good also as a structure using the gas barrier film manufactured with the manufacturing method of this invention for any one of these.
Further, a passivation film may be provided on the organic EL element 124.

Moreover, it is preferable that the to-be-transferred base material 102 of the gas barrier film 100 used for the organic EL element 124 is a retardation film.
This is preferable in that reflection from external light is prevented, migration is small, and high contrast can be realized.

FIG. 11 is an example of a wavelength conversion film in which a wavelength conversion layer is sealed using a gas barrier film produced by the production method of the present invention.
A wavelength conversion film 130 shown in FIG. 11 includes a wavelength conversion layer 132, a gas barrier film 100 laminated on one surface of the wavelength conversion layer 132, and a gas barrier film 100 laminated on the other surface of the wavelength conversion layer 132. Have.
That is, the wavelength conversion film 130 has a configuration in which the wavelength conversion layer 132 is sandwiched between two gas barrier films 100 manufactured by the manufacturing method of the present invention.

The wavelength conversion layer 132 has a function of converting and emitting the wavelength of incident light, and is, for example, a quantum dot layer formed by dispersing quantum dots in a binder such as a resin.
There are no particular limitations on the type of quantum dots contained in the quantum dot layer, and various known quantum dots may be appropriately selected according to the required wavelength conversion performance or 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 depending on the type of quantum dots, required performance, and the like.

  In addition, in the example shown in FIG. 11, although it was set as the structure which seals both surfaces of the wavelength conversion layer with the gas barrier film manufactured with the manufacturing method of this invention, it is not limited to this, One side of a wavelength conversion layer is this It is good also as a structure sealed with the gas barrier film produced with the manufacturing method of invention, and sealing the other with the conventional gas barrier film.

Moreover, it is preferable that the gas barrier film 100 used for the wavelength conversion film 130 has a light-diffusion layer, as shown to FIG. 8 (A) or FIG. 8 (B).
By using the gas barrier film 100 that has a light diffusion layer and the boundary of the transfer layer 30 is hardly visible, the optical characteristics can be further improved.

  As mentioned above, although the manufacturing method of the gas barrier film of this invention, the organic electroluminescent laminated body, and the wavelength conversion film were demonstrated in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the summary of this invention. Of course, various improvements and changes may be made.

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

[Example 1]
As Example 1, a gas barrier film 100 shown in FIG.

[Production of transfer-type gas barrier film (preparation process)]
First, a transfer type gas barrier film 10a as shown in FIG.

<Formation of release resin layer 20>
A long PET film (Toyobo Co., Ltd., Cosmo Shine A4100) having a width of 700 mm, a thickness of 50 μm, and a length of 100 m was used as the substrate 12.
A release resin layer 20 was formed on the uncoated surface side of the substrate 12 by the following procedure.

As the coating solution A1 to be the release resin layer 20, a coating solution prepared by dissolving a COC resin (APEL 6015T manufactured by Mitsui Chemicals, Inc.) with cyclohexane and having a solid content concentration of 10% was used.
The coating solution A1 is filled in the coating unit 40 of the RtoR film forming apparatus as shown in FIG. 9A, and a substrate roll Ra obtained by winding the substrate 12 in a roll shape is loaded at a predetermined position. Thus, the substrate 12 was inserted into a predetermined transport path. The coating unit 40 used a die coater.
Then, while the substrate 12 is conveyed in the longitudinal direction, the coating unit 40 applies the coating liquid A1 to the substrate 12 so that the dry film thickness is 2 μm, and the drying unit 42 has a drying temperature of 100 ° C. for 3 minutes. The release resin layer 20 was formed on the substrate 12 by drying. In this case, the curing part 44 was not used.
That is, the material for forming the release resin layer 20 is a cycloolefin copolymer.

<Formation of organic layer 14>
Next, the organic layer 14 was formed on the formed release resin layer 20 by the following procedure.
As coating liquid B1 to be the organic layer 14, A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a photopolymerization initiator (Irg819 manufactured by BASF Japan) are prepared, 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 film forming apparatus using RtoR as shown in FIG. 9A, and the substrate 12 (deposition substrate Za) having the release resin layer 20 is rolled. The rolled base material roll Rb was loaded at a predetermined position, and the film formation base material Za was inserted into a predetermined transport path. The coating unit 40 used a die coater.
Then, the coating liquid B1 is applied on the release resin layer 20 of the film forming substrate Za so as to have a dry film thickness of 1 μm while the film forming substrate Za is conveyed in the longitudinal direction. 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 (integrated irradiation amount of about 700 mJ / cm ² ) to be cured and the organic layer 14 on the release resin layer 20. Formed.
After the organic layer 14 was cured, it was wound up after a protective film 28 of polyethylene was pasted on the organic layer 14 before contacting the roll that first contacted the surface on the organic layer 14 side.

<Formation of inorganic layer 16>
Next, the inorganic layer 16 was formed on the formed organic layer 14 by the following procedure.
The substrate 12 (deposition base Zb) on which the release resin layer 20 and the organic layer 14 are formed is wound in a roll shape at a predetermined position in the supply chamber 50 of the film formation apparatus as shown in FIG. 9B. A base film roll Rc was loaded, and a protective film roll 29R was loaded at a predetermined position in the film forming chamber 52. Furthermore, the film-forming substrate Zb was sent out from the substrate roll Rc, and passed through a predetermined conveyance path from the supply chamber 50 to the winding chamber 54 through the film-forming chamber 52. Further, the protective film 29 was sent out from the protective film roll 29 </ b> R and passed through a predetermined transport path from the film forming chamber 52 to the winding chamber 54.
In this state, while the film-forming substrate Zb and the protective film 29 are conveyed synchronously, the protective film 28 is peeled from the film-forming substrate Zb after passing through the film surface touch roll immediately before film formation, and film formation is performed. A silicon nitride film was formed as the inorganic layer 16 by CCP-CVD on the surface of the organic layer 14 of the deposition target substrate Zb supported / guided by the drum 62 in the chamber 52. Next, the protective film 29 was laminated and pasted on the inorganic layer 16 by the laminated roller pair 72 to produce a transfer type gas barrier film 10a as shown in FIG.

In forming the inorganic layer 16, silane gas (flow rate 160sccm), ammonia gas (flow rate 370sccm), and hydrogen gas (flow rate 2000sccm) 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 film forming pressure was 40 Pa. The film thickness of the inorganic layer 16 was 30 nm.
The protective film 29 was attached after the inorganic layer 16 was formed and before the inorganic layer 16 was in contact with other members. Further, a polyethylene film was used as the protective film 29.

  The produced transfer type gas barrier film 10a was cut off at both ends 20 mm in the width direction so that the gas barrier layer 18 was formed in the entire width direction. That is, the width of the produced transfer gas barrier film 10a was 660 mm.

[First bonding step]
Next, in the first bonding step, the produced transfer gas barrier film 10 a was bonded to the transfer base material 102.
As the substrate to be transferred 102, a long Fujitack (TD80 manufactured by FUJIFILM Corporation) having a width of 1400 mm, a thickness of 80 μm, and a length of 50 m was used.
The transfer substrate 102 is used as a film formation substrate, set in an organic film formation apparatus as shown in FIG. 9A, and a coating liquid that becomes a 1380 mm wide adhesive layer on the transfer substrate 102 by RtoR. After applying C1 and drying at a drying temperature of 100 ° C. for 3 minutes to form an adhesive layer, instead of the protective film, the previous transfer-type gas barrier film was stuck on the adhesive layer in parallel in the width direction and wound up It was. That is, the transfer type gas barrier film is laminated with a width of 1320 mm.
The thickness of the adhesive layer was 2 μm.

As coating liquid C1 to be an adhesive layer, SK Dyne NT21 (manufactured by Soken Chemical Co., Ltd.) added with a curing agent L-45 (manufactured by Soken Chemical Co., Ltd.) in a ratio of 100: 2 is diluted with butyl acetate to obtain a solid. The concentration was adjusted to 15%.
This adhesive layer is an acrylic adhesive.

[Peeling process]
After the transfer-type gas barrier film is bonded and wound up, the substrate to be transferred 102 is stored at a temperature of 25 ° C. and a humidity of 50% RH for 3 days in order to stabilize the adhesion of the adhesive layer. The transfer barrier film substrate 12 was peeled off to produce a gas barrier film 100.

[Example 2]
Furthermore, the following 2nd sticking process and 2nd peeling process were performed, and it was set as the structure which transfers the transfer layer 30b on the transfer layer 30, and produces the gas barrier film which has two layers of transfer layers in the thickness direction In the same manner as in Example 1, a gas barrier film 110 as shown in FIG.

[Second sticking step]
First, one transfer-type gas barrier film 10a produced in Example 1 and two slits of the transfer-type gas barrier film 10a with a width of 330 mm were prepared.
The gas barrier film 100 produced in Example 1 is used as a film formation substrate, set in an organic film formation apparatus as shown in FIG. 9A, and applied to form a 1380 mm wide adhesive layer on the transfer layer 30 by RtoR. After the liquid C1 was applied and dried at a drying temperature of 100 ° C. for 3 minutes to form an adhesive layer, a transfer gas barrier film 10a having a width of 660 mm was formed at the center in the width direction, and a transfer gas barrier film 10a having a width of 330 mm was formed at both ends thereof. Sticked and wound up.

[Second peeling step]
As in the first peeling step, in order to stabilize the adhesive force of the adhesive layer, it was stored for 3 days at RT, and after aging, the substrate 12 of the transfer type barrier film was peeled off to produce a gas barrier film 110. .

[Example 3]
A gas barrier film 100 was produced in the same manner as in Example 1 except that the transfer gas barrier film 10b having the adhesive layer 24 as shown in FIG. 4A was used as the transfer gas barrier film.

[Production of transfer-type gas barrier film]
In the same manner as in Example 1, after the release resin layer 20, the organic layer 14, and the inorganic layer 16 were formed on the substrate 12, it was set in an organic film forming apparatus as shown in FIG. After coating the coating liquid C1 used as the adhesion layer 24 on the inorganic layer 16 and drying it at a drying temperature of 100 ° C. for 3 minutes to form the adhesion layer 24, a protective film 26 (Film Binder BD manufactured by Fujimori Kogyo Co., Ltd.) is applied. The transfer type gas barrier film 10b was prepared by sticking.

[First bonding step]
As in Example 1, except that the protective film 26 was peeled off from the transfer gas barrier film 10b and bonded to the transfer substrate 102 without applying the adhesive layer onto the transfer substrate 102. The transfer type gas barrier film 10b and the transfer target substrate 102 were bonded together.

[Example 4]
Furthermore, the following 2nd sticking process and 2nd peeling process were performed, and it was set as the structure which transfers the transfer layer 30b on the transfer layer 30, and produces the gas barrier film which has two layers of transfer layers in the thickness direction In the same manner as in Example 3, a gas barrier film 110 as shown in FIG.

[Second sticking step]
The transfer gas barrier film 10b produced in Example 3 was used, and the same procedure as in the second sticking step of Example 2 was performed except that the adhesive layer was not applied to the transfer substrate 102.

[Second peeling step]
The second peeling process in Example 2 was performed in the same manner.

[Example 5]
A gas barrier film was produced in the same manner as in Example 1 except that the refractive index adjusting layer forming step was performed after the peeling step.

[Refractive index adjusting layer forming step]
On the transfer layer 30 (release resin layer 20) of the gas barrier film 100 produced in Example 1, the following coating solution was applied and cured to form a refractive index adjusting layer having a thickness of 5 μm.
The coating liquid for the refractive index adjustment layer is obtained by adding a titanium oxide dispersion (HTD1061 manufactured by Teika Co., Ltd.) to A-DPH (manufactured by Shin-Nakamura Kogyo Co., Ltd.) and dispersing with MEK (methyl ethyl ketone). It was prepared to be 1.55.

[Example 6]
A gas barrier film was produced in the same manner as in Example 5 except that the refractive index adjusting layer was formed on the surface of the transfer substrate 102 on which the transfer layer 30 was not transferred.

[Example 7]
A gas barrier film was produced in the same manner as in Example 1 except that the light diffusion layer forming step was performed after the peeling step.

[Light diffusion layer forming step]
On the transfer layer 30 (peeling resin layer 20) of the gas barrier film 100 produced in Example 1, the following coating solution was applied and cured to form a 20 μm thick light diffusion layer.
The coating solution for the light diffusing layer is a urethane skeleton acrylic polymer (Acrit 8BR930 manufactured by Taisei Fine Chemical Co., Ltd.), silicone particles (Tospearl 130/1100 = 1: 1) as a light diffusing agent, and Irg184 (manufactured by BASF Japan) as a photopolymerization initiator. ) Was weighed at 30: 68: 2 and diluted with MIBK (methyl isobutyl ketone).

[Example 8]
A gas barrier film was produced in the same manner as in Example 7 except that a light diffusion layer was formed on the surface of the transfer substrate 102 on which the transfer layer 30 was not transferred.

[Example 9]
A light diffusion layer is formed in the same manner as in Example 7 on the surface opposite to the refractive index adjustment layer of the gas barrier film having the refractive index adjustment layer on the transfer layer 30 (peeling resin layer 20) produced in Example 5. Thus, a gas barrier film was produced.

[Example 10]
A gas diffusion layer was formed by forming a light diffusion layer in the same manner as in Example 7 on the surface opposite to the refractive index adjusting layer of the gas barrier film having a refractive index adjusting layer on the surface to which the transfer layer 30 was not transferred. A film was prepared.

[Example 11]
A gas barrier film was produced in the same manner as in Example 1 except that a barrier film (Tech Barrier L manufactured by Mitsubishi Plastics, Inc.) was used as the transfer base material 102 instead of Fujitac.

[Example 12]
A gas barrier film was produced in the same manner as in Example 1 except that instead of Fujitac, a special polycarbonate W138 (manufactured by Teijin Ltd.) was used as the substrate 102 to be transferred. The special polycarbonate W138 is a retardation film (1 / λ plate).

[Comparative Example 1]
A transfer type gas barrier film was prepared in the same manner as in Example 1 except that the release resin layer was not provided, and the transfer type gas barrier film was transferred to a transfer substrate to prepare a gas barrier film.
[Comparative Example 2]
Instead of the transfer type gas barrier film, a gas barrier film was produced in the same manner as in Example 1 except that a 12 μm-thick Tech Barrier L (manufactured by Mitsubishi Plastics Co., Ltd.) was aligned and adhered to the film formation substrate.

[Comparative Example 3]
A tech barrier L was further adhered to the gas barrier film produced in Comparative Example 2 to produce a gas barrier film having a structure having two tech barrier L layers.

[Evaluation]
About the produced gas barrier film of Examples 1-12 and Comparative Examples 1-3, gas barrier property and the visibility of a stripe were evaluated.

<Gas barrier properties>
The water vapor transmission rate of the gas barrier film was measured by a calcium corrosion method (a method described in JP-A-2005-283561). The conditions of the constant temperature and humidity treatment were a temperature of 40 ° C. and a relative humidity of 90% RH.
Based on the measured water vapor transmission rate, evaluation was performed 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 less than 1 × 10 ⁻⁴ [g / (m ² · day)] C: Water vapor transmission rate is 1 × 10 ⁻⁴ or more and less than 5 × 10 ⁻⁴ [g / (m ² · day)] D: Water vapor transmission rate is 5 × 10 ⁻⁴ or more and 1 × 10 ⁻³ [g / (m Less than ² · day)] E: Water vapor transmission rate is 1 × 10 ^-3 [g / (m ² · day)] or more

Further, when the water vapor transmission rate (WVTR) of the substrate 102 alone was measured in the same manner, the water vapor transmission rate of Fujitac alone was 400 [g / (m ² · day)], and a barrier film (manufactured by Mitsubishi Plastics, Inc.). Tech barrier L) has a water vapor transmission rate of 0.5 [g / (m ² · day)], and special polycarbonate W138 (manufactured by Teijin Limited) has a water vapor transmission rate of 140 [g / (m ² · day)]. It was.

<Visibility of streaks>
Light was applied from one side of the produced gas barrier film and visually observed from the opposite side to evaluate whether or not the boundary of the transfer layer 30 was visually recognized as a streak.
A: Streaks are not visually recognized B: Streaks appear to be faint intermittently C: Streaks appear to be linearly thin D: Streaks are clearly visible The results are shown in the following table.

As shown in Table 1 above, it can be seen that the examples produced by the production method of the present invention are superior in gas barrier properties as compared with the comparative examples.
From the comparison between Example 1 and Example 2 and the comparison between Example 3 and Example 4, it is preferable to further include a second bonding step of bonding a transfer type gas barrier film on the transfer layer. I understand that.
Moreover, it turns out that the visibility of a stripe can be reduced by having the process of forming a refractive index adjustment layer or a light-diffusion layer from Examples 5-10.
Further, from comparison with Examples 1, 11, and 12, it is found that the water vapor transmission rate of the substrate to be transferred is preferably 0.5 [g / (m ² · day)] or less.

[Example 13]
An organic EL laminate was produced using the produced gas barrier film.

<Production 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.
The periphery 2 mm of this element substrate was masked with ceramic. Further, the element substrate subjected to masking was loaded into a general vacuum deposition apparatus, an electrode made of metal aluminum having a thickness of 100 nm was formed by vacuum deposition, and a lithium fluoride layer having a thickness of 1 nm was further formed. . Next, the following organic compound layers were sequentially formed by vacuum deposition on the element substrate on which the electrode and the lithium fluoride layer were formed.
(Light emitting layer / electron transport 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: film thickness 10 nm
Further, the element substrate on which these layers are formed is loaded into a general sputtering apparatus, and an ITO thin film having a thickness of 0.2 μm is formed by DC magnetron sputtering using ITO (Indium Tin Oxide indium tin oxide) as a target. The transparent electrode which consists of was formed, and the organic EL element 124 which is a light emitting element using an organic EL material was formed.

<Sealing with gas barrier film>
Next, the masking was removed from the element substrate on which the organic EL element 124 was formed. An acrylic adhesive was applied to the element substrate from which the masking was removed, and the gas barrier film 100 of Example 1 was bonded.

[Example 14]
An organic EL laminate was produced in the same manner as in Example 13 except that the gas barrier film with retardation produced in Example 10 was used instead of the gas barrier film 100 of Example 1.

[Evaluation]
Durability evaluation was performed about the produced organic electroluminescent laminated body of Example 13 and 14. FIG.

Specifically, the produced organic EL laminate was left in an environment of a temperature of 60 ° C. and a humidity of 90% RH for 200 hours. After being allowed to stand, each organic EL laminate was made to emit light by applying a voltage of 7 V using an SMU2400 type source measure unit manufactured by Keithell. Observation with a microscope from the gas barrier film side, the presence or absence of dark spots was confirmed and evaluated according to the following criteria.
A: Generation of dark spots was not observed at all B: Generation of dark spots was slightly observed C: Generation of dark spots was clearly recognized D: Area ratio of dark spots was larger Evaluation As a result, the organic EL laminates of Examples 11 and 12 were all A.

[Example 15]
A wavelength conversion film 130 as shown in FIG. 11 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 to be 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 (light emission maximum: 520 nm) 10.0 parts by mass-Toluene dispersion of quantum dot 2 (light emission maximum: 630 nm) 1.0 part by weight-80.8 parts by weight of lauryl methacrylate-Trimethylolpropane 18.2 parts by mass of triacrylate / 1.0 part by mass of photopolymerization initiator (Irgacure 819 (manufactured by BASF))

<Preparation of quantum dot film>
Using the gas barrier film of Example 1 as the first film, the coating composition prepared above was coated on the release resin layer 20 with a die coater while being continuously conveyed at a tension of 1 m / min and 60 N / m, A coating film having a thickness of 50 μm was formed.
Next, the film on which the coating film is formed is wound around a backup roller, and a second film (having the same structure as the first film) is laminated on the coating film so that the release resin layer 20 is in contact with the coating film. The coating film was sandwiched between the first film and the second film.
While continuously transporting in this state, after passing through a heating zone at 60 ° C. for 3 minutes, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), curing by irradiating with ultraviolet rays, quantum dots The quantum dot layer (wavelength conversion layer 132) containing was formed, and the quantum dot film (wavelength conversion film 130) was produced. The irradiation amount of ultraviolet rays was 2000 mJ / cm ² .

[Example 16]
A wavelength conversion film 130 was produced in the same manner as in Example 15 except that the gas barrier film with a light diffusion layer of Example 7 was used as the first film.

[Evaluation]
Durability evaluation was performed about the produced wavelength conversion film of Example 15 and 16.

Specifically, the luminance of the wavelength conversion film immediately after production and the luminance after being left in an environment of a temperature of 60 ° C. and a humidity of 90% RH for 1000 hours were measured, and durability was evaluated from the amount of change.
The measurement of luminance was performed as follows.
First, a commercially available liquid crystal display device (Amazon Kindle Kindle Fire HDX 7 ") was disassembled, and a backlight unit with a blue light source was taken out. Next, a wavelength conversion film cut into a rectangle on the light guide plate of the backlight unit The two prism sheets taken out from the liquid crystal display device 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 surface of the backlight unit.

As a result of the measurement, in both Examples 15 and 16, 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 produced with the manufacturing method of this invention has high durability.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10 Transfer type gas barrier film 12 Substrate 14 Organic layer 16 Inorganic layer 18 Gas barrier layer 20 Peeling resin layer 24 Adhesive layer 26, 28, 29 Protective film 30 Transfer layer 40 Application part 42 Drying part 44 Curing part 48, 49 Conveying roller pair 50 Supply Chamber 50a, 52a, 54a Vacuum evacuation 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, 110 Gas barrier film 102 Transfer base Material 104 Optical functional layer 120 Organic EL laminate 124 Organic EL element 126 Adhesive layer 130 Wavelength conversion film 132 Wavelength conversion layer

Claims (13)

A substrate, a gas barrier layer having one or more combinations of an inorganic layer and an organic layer to be a formation surface of the inorganic layer provided on one surface of the substrate, and provided between the substrate and the gas barrier layer; A transfer film preparation step of preparing a transfer type gas barrier film having a release resin layer for closely adhering to the organic layer and peeling from the substrate;
A first laminating step in which two or more transfer-type gas barrier films are arranged in a surface direction on a substrate to be transferred, and the gas barrier layer side is bonded to the substrate to be transferred; and
A method for producing a gas barrier film, comprising a peeling step of peeling the substrate of the transfer type gas barrier film from the release resin layer.   The gas barrier film according to claim 1, further comprising an adhesive layer forming step of forming an adhesive layer on the gas barrier layer side of the transfer type gas barrier film or on the transferred substrate side before the first bonding step. Manufacturing method.   After the peeling step, the transfer-type gas barrier film is further bonded to the transfer layer including the gas barrier layer and the release resin layer that are bonded to the transfer base material and peeled off the substrate. The manufacturing method of the gas barrier film of Claim 1 or 2 which has a bonding process.   The bonding position of the transfer type gas barrier film to be bonded in the second bonding step is a position different from the bonding position in the first bonding step in the surface direction of the transferred substrate. The manufacturing method of the gas barrier film of description.   The distance between the end surfaces of the transfer layer comprising the gas barrier layer and the release resin layer, which are bonded to each other on the transfer base material and peeled off the substrate, is 1 mm or less, or 3 mm or less. The manufacturing method of the gas barrier film as described in any one of Claims 1-4 which overlaps with the width | variety.   Refractive index for forming a refractive index adjusting layer on at least one of the surface of the substrate to be transferred opposite to the surface on which the transfer gas barrier film is bonded and the release resin layer of the transfer gas barrier film The manufacturing method of the gas barrier film as described in any one of Claims 1-5 which has an adjustment layer formation process.   The said refractive index adjustment layer consists of titanium, aluminum, zirconia, and the mixture containing the microparticles | fine-particles which consist of at least 1 of these oxides, and an acryl or urethane. Of manufacturing a gas barrier film.   A light diffusing layer that forms a light diffusing layer on at least one of the surface of the substrate to be transferred opposite to the surface on which the transfer gas barrier film is bonded and the release resin layer of the transfer gas barrier film The manufacturing method of the gas barrier film as described in any one of Claims 1-7 which has a formation process.   The method for producing a gas barrier film according to any one of claims 1 to 8, wherein the light diffusion layer comprises particles serving as a diffusing material and a resin serving as a binder. The method for producing a gas barrier film according to any one of claims 1 to 9, wherein a water vapor permeability of the substrate to be transferred is less than 0.5 g / (m ² · day).   The method for producing a gas barrier film according to claim 1, wherein the substrate to be transferred is a retardation film.   The method for producing a gas barrier film according to any one of claims 1 to 11, wherein a material for forming the release resin layer is a cyclic olefin resin having a glass transition temperature Tg of 100 ° C or higher.   The method for producing a gas barrier film according to claim 12, wherein a material for forming the release resin layer is a cycloolefin copolymer.

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